Organic compounds

ABSTRACT

Compounds of formula                    
     (I), wherein 
     either X is CH or N, Y is OR 1  and Z is O, or 
     X is N, Y is NHR 8  and Z is O, S or S(═O); 
     R 1 , R 2  and R 3  are as defined according to the specification; m is 0, 1 or 2; 
     R 5  is, for example, halogen, C 1 -C 6 alkyl, halo-C 1 -C 6 alkyl or C 3 -C 6 cycloalkyl; 
     n is 0, 1, 2, 3 or 4; R 9  is methyl, fluoromethyl or difluoromethyl; 
     A and R 7  are as defined according to the specification; 
     D is O, S, —S(═O) or S(═O) 2 ; G is C 1 -C 6 aalkylene; 
     T—R 6  is R 6 , —C(═N—O—A 1 —R 77 )—R 6 ; —SiR 14 (R 15 )—R 6 ; —C(═O)—R 6 ; —C(R 16 )═C(R 17 )—R 6 , —C≡C—R 6  or 
     —D—R 6 ; 
     R 6  is C 1 -C 4 alkyl or unsubstituted or substituted aryl or heteroaryl; 
     A 1  and R 77  are as defined above for A and R 7 ; 
     L is U—R 18 , P(OR) v R 11 R 12 , P(S) w R 11 R 12  or N(aryl)R 13 ; v and w are 0 or 1; 
     U—R 18  is —C(═O)—C(═O)—R 18 ; —C(OH)—C(OH)—R 18 ; —C(═N—O—A 1 —R 7 )—R 18 ;                    
     a is 0 or 1; b is 0 or 1; 
     R 11 , R 12  and R 13  are, for example, C 1 -C 6 alkyl, halo-C 1 -C 6 alkyl or C 3 -C 6 cycloalkyl; 
     R 14  and R 15  are each independently of the other C 1 -C 4 alkyl; 
     R 16  and R 17  are each independently of the other hydrogen, C 1 -C 4 alkyl or halogen and R 18  is R 5 ; 
     and, where applicable, their possible E/Z isomers, mixtures of E/Z isomers and/or tautomers, in each case in free form or in salt form, a method of controlling pests, a process for the preparation of those compounds and their use are described.

ORGANIC COMPOUNDS

The invention relates to compounds of formula

wherein either

X is CH or N, Y is OR, and Z is O, or

X is N, Y is NHR₈ and Z is O, S or S(═O);

R₁ is hydrogen or C₁-C₄alkyl;

R₈ is hydrogen or C₁-C₄alkyl;

R₂ is H, C₁-C₄alkyl, halo-C₁-C₄alkyl, C₃-C₆cycloalkyl,C₁-C₄alkoxymethyl, C₁-C₄alkoxy, halo-C₁-C₄alkoxy, C₁-C₄alkylthio,halo-C₁-C₄alkylthio or CN;

R₃ and R₄ are each independently of the other H, C₁-C₄alkyl,C₁-C₄alkoxy, OH, CN, NO₂, a (C₁-C₄alkyl)₃—Si group, the alkyl groupsbeing the same or different, halogen, (C₁-C₄alkyl)S(═O)_(m),(halo-C₁-C₄alkyl)S(═O)_(m), halo-C₁-C₄alkyl or halo-C₁-C₄alkoxy;

m is 0, 1 or 2;

R₅ independently of any other is halogen, C₁-C₆alkyl, halo-C₁-C₆alkyl,C₃-C₆cycloalkyl, halo-C₃-C₆cycloalkyl, C₁-C₆alkoxy, halo-C₁-C₆alkoxy,C₁-C₆alkylthio, halo-C₁-C₆alkylthio, C₁-C₆alkylsulfinyl,halo-C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, halo-C₁-C₆alkylsulfonyl,C₁-C₆alkylsulfonyloxy, halo-C₁-C₆alkylsulfonyloxy,C₁-C₆alkoxy-C₁-C₆alkyl, halo-C₁-C₆alkoxy-C₁-C₆alkyl,C₁-C₆alkylthio-C₁-C₆alkyl, halo-C₁-C₆alkylthio-C₁-C₆alkyl,C₁-C₆alkylsulfinyl-C₁-C₆alkyl, halo-C₁-C₆alkylsulfinyl-C₁-C₆alkyl,C₁-C₆alkylsulfonyl-C₁-C₆alkyl, halo-C₁-C₆alkylsulfonyl-C₁-C₆alkyl,C₁-C₆alkylcarbonyl, halo-C₁-C₆alkylcarbonyl, C₁-C₆-alkoxycarbonyl,halo-C₁-C₆alkoxycarbonyl, C₁-C₆alkylaminocarbonyl,C₁-C₄alkoxyiminomethyl, di(C₁-C₆alkyl)aminocarbonyl, the alkyl groupsbeing the same or different; C₁-C₆alkylaminothiocarbonyl,di(C₁-C₆alyl)aminothiocarbonyl, the alkyl groups being the same ordifferent; C₁-C₆alkylamino, di(C₁-C₆alkyl)amino, the alkyl groups beingthe same or different; NO₂, CN, SF₅, thioamido, thiocyanatomethyl,trimethylsilyl; C₁-C₄alkylenedioxy or —CH═CH—CH═CH— each of which isunsubstituted or, depending on its substitution possibilities, mono- totetra-substituted, the substituents of the C₁-C₄alkylenedioxy or—CH═CH—CH═CH— group being selected from the group consisting ofC₁-C₄alkyl and halogen; a heterocyclyl, aryl-Q-C₁-C₆alkyl,aryl-Q—C₂-C₆alkenyl, heterocyclyl-Q—C₁-C₆alkyl orheterocyclyl-Q—C₂-C₆-alkenyl, or aryl-Q—, heterocycylyl-Q—,aryl-Q—C₁-C₆alkyl, aryl-Q—C₂-C₆alkenyl, heterocyclyl-Q—C₁-C₆-alkyl orheterocyclyl-Q—C₂-C₆alkenyl each of which is, depending on itssubstitution possibilities, mono- to penta-substituted in the aryl orheterocyclyl ring, the substituents being selected independently of oneanother from the group consisting of halogen, C₁-C₆alkyl,halo-C₁-C₆alkyl, C₃-C₆cycloalkyl, halo-C₃-C₆cycloalkyl, C₁-C₆alkoxy,halo-C₁-C₆alkoxy, CN, nitro and C₁-C₆alkoxycarbonyl; and, when n isgreater than 1, the radicals R₅ are the same or different;

n is 0, 1, 2, 3 or, if either a or b is 0, 4;

Q is a direct bond, —CH(OH)—, —C(═O), —S—, —S(═O) or —S(═O)₂;

R₉ is methyl, fluoromethyl or difluoromethyl; either

A is a direct bond, C₁-C₁₀alkylene, —C(═O)—, —C(═S)— orhalo-C₁-C₁₀alkylene and

R₇ is a radical R₁₀; or

A is C₁-C₁₀alkylene, —C(═O)—, —C(═S) or halo-C₁-C₁₀alkylene and

R₇ is —CN, OR₁₀, N(R₁₀)₂, the radicals R₁₀ being the same or different,—SR₁₀, —S(═O)R₁₀ or —S(═O)₂R₁₀

R₁₀ is H, C₁-C₆alkyl, C₂-C₆alkenyl, C₂-C₆alkynyl or C₃-C₆cycloalkyl, orC₁-C₆alkyl, C₂-C₈-alkenyl, C₂-C₈alkynyl or C₃-C₆cycloalkyl each mono- orpoly-substituted by substituents from the group consisting of halogen;—Si(C₁-C₄alkyl)₃, the alkyl groups being the same or different;C₁-C₆alkoxycarbonyl or an aryl or heterocyclyl group that isunsubstituted or mono- or poly-substituted by substituents selected fromthe group consisting of halogen, C₁-C₄alkyl and halo-C₁-C₄alkyl; and

D is O, S, —S(═O) or S(═O);

G is C₁-C₈alkylene;

T—R₆ is R₆; —C(═N—O—A₁—R₇₇)—R₆; —SiR₁₄(R₁₅)—R₆; —C(═O)—R₆;C(R₁₆)═C(R₁₇)—R₆; —C≡C—R₆ or —D—R₆;

R₆ is C₁-C₄alkyl, aryl or heteroaryl; or aryl or heteroaryl each ofwhich—depending on the substitution possibilities on the ringstructure—is mono- to penta-substituted by substituents selectedindependently of one another from the group consisting of (R₅)_(s); is,depending on the substitution possibilities on the ring, 0, 1, 2, 3, 4or 5, the substituents R₅ being independent of one another when s isgreater than 1;

A₁ and R₇₇ are as defined above for A and R₇;

a is 0 or 1;

L is U—R₁₈, P(O)_(v)R₁₁R₁₂, P(S)_(w)R₁₁R₁₂ or N(aryl)R₁₃, the arylradical being either unsubstituted or mono- to penta-substituted bysubstituents selected independently of one another from the groupconsisting of R₅;

v and ware 0 or 1;

U—R₁₈ is —C(═O)—C(═O)—R₁₈; —C(OH)—C(OH)—R₁₈; —C(═N—O—A₁—R₇)—R₁₈;

p is from 0 to4;

R₁₁ and R₁₂ are each independently of the other C₁-C₆alkyl,halo-C₁-C₆alkyl, C₃-C₆cycloalkyl, halo-C₃-C₆cycloalkyl, C₁-C₆alkoxy,halo₁-C₆alkoxy, C₁-C₆alkylthio, halo-C₁-C₆alkylthio, aryl, heteroaryl,aryloxy, arylthio, heteroaryloxy or heteroarylthio; or aryl, heteroaryl,aryloxy, arylthio, heteroaryloxy or heteroarylthio each mono- topenta-substituted by R₅, the substituents R₅ being independent of oneanother;

b is 0 or 1, but a and b are not simultaneously 0;

R₁₃ is hydrogen, C₁-C₆alkyl, halo-C₁-C₆alkyl, C₃-C₆cycloalkyl,halo-C₃—C₆-cycloalkyl, C₁-C₆alkylsulfinyl, halo-C₁-C₆alkylsulfinyl,C₁-C₆alkylsulfonyl, halo-C₁-C₆alkylsulfonyl, C₁-C₆alkoxy-C₁-C₆alkyl,halo-C₁-C₆alkoxy-C₁-C₆alkyl, C₁-C₆alkylthio-C₁-C₆alkyl,halo-C₁-C₆alkylthio-C₁-C₆alky, C₁-C₆alkylsulfinyl-C₁-C₆alkyl,halo-C₁-C₆alkylsulfinyl-C₁-C₆alkyl, C₁-C₆alkylsulfonyl-C₁-C₆alkyl,halo-C₁-C₆alkylsulfonyl-C₁-C₆alkyl, formyl, C₁-C₆alkylcarbonyl,C₁-C₆alkyl-C(═S)—, C₁-C₆alkylthio-C(═S)—, halo-C₁-C₆alkylcarbonyl,C₁-C₆alkoxycarbonyl, halo-C₁-C₆alkoxycarbonyl, C₁-C₆alkylaminocarbonyl,C₁-C₄-alkoxyiminomethyl, di(C₁-C₆alkyl)aminocarbonyl, the alkyl groupsbeing the same or different; C₁-C₆alkylaminothiocarbonyl,di(C₁-C₆alkyl)aminothiocarbonyl, the alkyl groups being the same ordifferent; C₁-C₆alkyldicarbonyl, halo-C₁-C₆alkyldicarbonyl,C₁-C₆alkoxydicarbonyl, halo-C₁-C₆alkoxydicarbonyl,C₁-C₆alkylaminodicarbonyl, di(C₁-C₆alkyl)aminodicarbonyl, the alkylgroups being the same or different; C₁-C₆alkylaminodithiocarbonyl,di(C₁-C₆alkyl)aminodithiocarbonyl, the alkyl groups being the same ordifferent; aryl, arylsulfinyl, aryl-C₁-C₆alkylsulfinyl, arylsulfonyl,aryl-C₁-C₆alkyl-sufonyl, aryloxy-C₁-C₆alkyl, arylthio-C₁-C₆alkyl,aryl-C₁-C₆alkylsulfinyl-C₁-C₆alkyl, aryl-C₁-C₆alkylsulfonyl-C₁-C₆alkyl,arylcarbonyl, arylalkylcarbonyl, aryloxycarbonyl, arylalkoxycarbonyl,arylaminocarbonyl, aryloxyiminomethyl, di(aryl)aminocarbonyl, the arylgroups being the same or different; arylaminothiocarbonyl,di(aryl)aminothiocarbonyl, the aryl groups being the same or different;aryldicarbonyl, aryl-C₁-C₆alkyldicarbonyl, aryloxydicarbonyl,aryl-C₁-C₆alkoxydicarbonyl, arylaminodicarbonyl,di(aryl)aminodicarbonyl, the aryl groups being the same or different;arylaminodithiocarbonyl, di(arylaminodithiocarbonyl, the aryl groupsbeing the same or different; and the aryl groups in the afore-mentionedsubstituents being unsubstituted or mono- to penta-substituted bysubstituents R₅, the substituents R₅ being independent of one another;unsubstituted or substituted heteroaryl, unsubstituted or substitutedheteroarylcarbonyl, unsubstituted or substituted heteroarylsulfinyl, orunsubstituted or substituted heteroarylsulfonyl;

R₁₄ and R₁₅ are each independently of the other C₁-C₄alkyl;

R₁₆ and R₁₇ are each independently of the other hydrogen, C₁-C₄alkyl orhalogen and R₁₈ is R₆;

and, where applicable, their possible E/Z isomers, mixtures of E/Zisomers and/or tautomers, in each case in free form or in salt form,

with the proviso (P1) that G is not —CH₂— when R₂ is methyl, R₃ and R₄are hydrogen, D is oxygen, a is 1, b is 0, and either in the group—SiR₁₄(R₁₄(R₁₅)—R₆ the radicals R₁₄, R₁₅ and R₆ are methyl, or in thegroup —C(R₁₆)═C(R₁₇)—R₆ the radical R₆ is methyl and the radical R₁₇ ishydrogen or methyl;

with the proviso (P2) that G is not C₁C₃alkylene when a is 1, b is 0, Tis a direct bond and R₆ is C₁-C₄alkyl;

and with the further proviso (P3) that G is not —CH₂— when D is oxygen,a is 1, b is 0, R₂ is C₁-C₆alkyl or C₃-C₆cycloalkyl, T is a direct bondand R₆ is unsubstituted or substituted phenyl;

to pesticidal compositions, the active ingredient of which is selectedfrom those compounds, E/Z isomers and tautomers, in each case in freeform or in salt form; to a process for the preparation of thosecompositions and to the use thereof; to intermediates and, whereapplicable, their possible E/Z isomers, mixtures of E/Z isomers and/ortautomers, in free form or in salt form, for the preparation of thosecompounds, where applicable tautomers, in free form or in salt form, ofthose intermediates; and to a process for the preparation of thoseintermediates and their tautomers and to the use thereof.

In the literature a number of methoxyacrylic acid derivatives areproposed as active ingredients in pesticides. The biological propertiesof those known compounds are not, however, entirely satisfactory in thefield of pest control and there is therefore a need to provide furthercompounds having pesticidal properties, especially for controllinginsects and representatives of the order Acarina and especially forcontrolling phytopathogenic microorganisms. That problem is solvedaccording to the invention by the provision of the present compounds offormula (I).

A number of compounds of formula (I), and of the formulae (III), (IV),(VI), (VIII), (IX), (XII), (XIII), (XV), (XVIII), (XXII), (XXIII) and(XXIV) given hereinafter, contain asymmetrical carbon atoms, as a resultof which the compounds may occur in optically active form. By virtue ofthe presence of the C═X and oximino double bonds, the compounds mayoccur in the E and Z isomeric forms. Atropisomers of the compounds mayalso occur. The corresponding formulae are intended to include all thosepossible isomeric forms and also mixtures thereof, for example racematesor mixtures of E/Z isomers, and also, where applicable, salts thereof,even if this is not specifically mentioned every time.

Unless indicated to the contrary, the general terms used hereinbeforeand hereinafter have the following meanings.

Unless indicated to the contrary, carbon-containing groups and compoundseach contain from 1 up to and including 8, especially from 1 up to andincluding 6, more especially from 1 up to and including 4, veryespecially 1 or 2, carbon atoms.

Alkyl, as a group per se and also as a structural unit of other groupsand compounds, such as of haloalkyl, alkoxy, alkylthio, alkylsulfinyl,alkylsulfonyl, alkylcarbonyl, alkoxycarbonyl, alkylamino,alkoxyiminomethyl, alkylaminocarbonyl and alkylaminothiocarbonyl, is, ineach individual case giving due consideration to the number of carbonatoms contained in the group or compound in question, eitherstraight-chain, that is to say methyl, ethyl, propyl, butyl, pentyl orhexyl, or branched, e.g. isopropyl, isobutyl, sec-butyl, tert-butyl,isopentyl, neopentyl or isohexyl.

Alkenyl, as a group per se and also as a structural unit of other groupsand compounds, such as of haloalkenyl, is, in each individual casegiving due consideration to the number of carbon atoms contained in thegroup or compound in question, either straight-chain, for example vinyl,1-methylvinyl, allyl, 1-butenyl or 2-hexenyl, or branched, for exampleisopropenyl.

Alkynyl, as a group per se and also as a structural unit of other groupsand compounds, such as of haloalkynyl, is, in each individual casegiving due consideration to the number of carbon atoms contained in thegroup or compound in question, either straight-chain, for examplepropargyl, 2-butynyl or 5-hexynyl, or branched, for example2-ethynylpropyl or 2-propargylisopropyl.

C₃-C₆Cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

Alkylene, as a group per se and also as a structural unit of othergroups and compounds, such as of haloalkylene, is, in each individualcase giving due consideration to the number of carbon atoms contained inthe group or compound in question, either straight-chain, for example—CH₂CH₂—, —CH₂CH₂CH₂— or —CH₂CH₂CH₂CH₂—, or branched, for example—CH(CH₃)—, —CH(C₂H₅)—, —C(CH₃)₂—, —CH(CH₃)CH₂— or —CH(CH₃)CH(CH₃)—.Preference is given to —CH₂CH₂—, —CH(CH₃)—, —CH(C₂H₅)—, and —CH₂CH₂CH₂—.

Aryl is phenyl or naphthyl, especially phenyl.

Heterocyclyl is a 5- to 7-membered aromatic or nonaromatic ring havingfrom one to three hetero atoms selected from the group consisting of N,O and S. Preference is given to aromatic 5- and 6-membered rings havinga nitrogen atom as hetero atom and optionally a further hetero atom,preferably nitrogen or sulfur, especially nitrogen. Preferred heteroarylmoieties are pyrazinyl, 3′-pyridyl, 2′-pyridyl, 4-pyridyl,2′-pyrimidinyl, 4′-pyrimidinyl, 5′-pyrimidinyl, 2′-thiazolyl,2′-oxazolyl, 2′-thienyl, 3′-thienyl and 2′-thiazolyl.

Halogen, as a group per se and also as a structural unit of other groupsand compounds, such as of haloalkyl, haloalkenyl and haloalkynyl, isfluorine, chlorine, bromine or iodine, especially fluorine, chlorine orbromine, more especially fluorine or chlorine, very especially fluorine.Halo-substituted carbon-containing groups and compounds, such ashaloalkyl, haloalkenyl or haloalkynyl, may be partially halogenated orper-halogenated, it being possible in the case of poly-halogenation forthe halogen substituents to be the same or different. Examples ofhaloalkyl, as a group per se and also as a structural unit of othergroups and compounds, such as of haloalkenyl, are methyl that is mono-to tri-substituted by fluorine, chlorine and/or by bromine, such as CHF₂or CF₃; ethyl that is mono- to penta-substituted by fluorine, chlorineand/or by bromine, such as CH₂CF₃, CF₂CF₃, CF₂CC₁ ₃, CF₂CHCl₂, CF₂CHF₂,CF₂CFCl₂, CF₂CHBr₂, CF₂CHClF, CF₂CHBrF or CClFCHClF; propyl or isopropylthat is mono- to hepta-substituted by fluorine, chlorine and/or bybromine, such as CH₂CHBrCH₂Br, CF₂CHFCF₃, CH₂CF₂CF₃ or CH(CF₃)₂; andbutyl, or an isomer thereof, that is mono- to hepta-substituted byfluorine, chlorine and/or by bromine, such as CF(CF₃)CHFCF₃ orCH₂(CF₂)₂CF₃. Haloalkenyl is, for example, CH₂CH═CHCl, CH₂CH═CCl₂,CH₂CF═CF₂ or CH₂CH═CHCH₂Br. Haloalkynyl is, for example, CH₂C≡CF,CH₂C≡CCH₂Cl or CF₂CF₂C≡CCH₂F.

A number of compounds of formula (I), and of the formulae (III) to(XXIV) given hereinafter, may, as is known to the person skilled in theart, be present in the form of tautomers, especially when R₇ is H.Hereinbefore and hereinafter any reference to these compounds shouldtherefore be understood as including also corresponding tautomers, evenwhen the latter are not specifically mentioned in each case.

Compounds of formula (I), and of the formulae (III) to (XXIV) givenhereinafter, that have at least one basic centre may, for example, formacid addition salts. Such salts are formed, for example, with stronginorganic acids, such as mineral acids, e.g. perchloric acid, sulfuricacid, nitric acid, nitrous acid, a phosphoric acid or a hydrohalic acid,with strong organic carboxylic acids, such as unsubstituted orsubstituted, for example halo-substituted, C₁-C₄alkanecarboxylic acids,e.g. acetic acid, saturated or unsaturated dicarboxylic acids, e.g.oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid orphthalic acid, hydroxycarboxylic acids, e.g. ascorbic acid, lactic acid,malic acid, tartaric acid or citric acid, or benzoic acid, or withorganic sulfonic acids, such as unsubstituted or substituted, forexample halo-substituted, C₁-C₄alkane- or aryisulfonic acids, e.g.methane- or p-toluene-suffonic acid. Furthermore, compounds of formula(I) having at least one acid group may form salts with bases. Suitablesalts with bases are, for example, metal salts, such as alkali metal oralkaline earth metal salts, e.g. sodium, potassium or magnesium salts,or salts with ammonia or an organic amine, such as morpholine,piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, e.g.ethyl-, diethyl-, triethyl or dimethyl-propyl-amine, or a mono-, di- ortri-hydroxy-lower alkylamine, e.g. mono-, di- or tri-ethanolamine. Itmay also be possible for corresponding internal salts to be formed.Within the context of the invention, preference is given toagrochemically advantageous salts; also included, however, are saltswhich cannot be agrochemically used, which are used however, forexample, for isolating and/or purifying free compounds of formula (I) oragrochemically acceptable salts thereof. Hereinbefore and hereinafterany reference to the compounds of formula (I) in free form is to beunderstood as including also the salts of compounds of formula (I), andany reference to the salts is to be understood as including also thecorresponding free compounds of formula (I), as appropriate andexpedient. The same applies also to tautomers of compounds of formulae(I) and (III) to (XXIV) and salts thereof. In each case the free form isgenerally preferred.

Preferred embodiments within the context of the invention, in each casetaking into consideration the provisos mentioned hereinbefore, are:

(1) a compound of formula (I) wherein X is CH and Z is O; especiallywherein X is CH, Z is O and Y is —OCH₃;

(2) a compound of formula (I) wherein X is N and Z is O; especiallywherein X is N, Z is O and Y is NHCH₃;

(3) a compound of formula (I) wherein Y is OC₁-C₄alkyl, preferablyC₁—C₂alkoxy, especially methoxy;

(4) a compound of formula (I) wherein

R₂ is H, C₁-C₄alkyl, halo-C₁-C₄alkyl or C₃-C₆cycloalkyl, preferablyC₁-C₄alkyl or halo-C₁-C₄alkyl, especially C₁-C₂alkyl, more especiallymethyl;

(5) a compound of formula (I) wherein

R₃ is H, C₁-C₄alkyl, C₁-C₄alkoxy, OH, CN, NO₂, halogen, halo-C₁-C₄alkylor halo-C₁-C₄alkoxy, preferably H, C₁-C₄alkyl, C₁-C₄alkoxy or halogen,especially H, methyl, methoxy, chlorine or fluorine, more especially H;

(6) a compound of formula (I) wherein

R₄ is H, C₁-C₄alkyl, C₁-C₄alkoxy, OH, CN, NO₂, halogen, halo-C₁-C₄alkylor halo-C₁-C₄alkoxy, preferably H, C₁-C₄alkyl, C₁-C₄alkoxy or halogen,especially H, methyl, methoxy, chlorine or fluorine, more especially H;

(7) a compound of formula (I) wherein

R₈ is H or C₁-C₂alkyl, preferably C₁-C₂alkyl, especially methyl;

(8) a compound of formula (I) wherein R₉ is methyl or fluoromethyl,preferably methyl;

(9) a compound of formula (I) wherein

A is a direct bond, C₁-C₁₀alkylene or halo-C₁-C₁₀alkylene, preferably adirect bond or C₁-C₄alkylene, especially a direct bond or methylene, andR₇ is a radical R₁₀;

(10) a compound of formula (I) wherein AR₇ is methyl or ethyl,especially ethyl;

(11) a compound of formula (I) wherein n is 0;

(12) a compound of formula (I) wherein a is 0, b is 1 and L is—C(═O)—C(═O)—R₁₈, —C(═NO—A₁—R₇₇)—R₁₈,

(13) a compound of formula (I) wherein R₁₈ is unsubstituted orsubstituted phenyl;

(14) a compound of formula (I) wherein a is 0, n is 0, b is 1 and L isPOR₁₁R₁₂;

(15) a compound of formula (I) wherein R₁, and R₁₂ are eachindependently of the other C₁-C₆alkoxy, halo-C₁-C₆alkoxy,C₁-C₆alkylthio, halo-C₁-C₆alkylthio, aryl, aryloxy or arylthio;

or aryl, heteroaryl, aryloxy, arylthio, heteroaryloxy or heteroarylthioeach mono- to tri-substituted by R₅, the substituents R₅ beingindependent of one another;

(16) a compound of formula (I) wherein a is 0, n is 0, b is 1, L isN(aryl)R₁₃ and R₁₃ is H, methyl, ethyl or formyl, especially H;

(17) a compound of formula (I) wherein a is 1, n is 0, b is 0 and D isoxygen;

(18) a compound of formula (I) wherein a is 1 and G is C₁-C₄alkylene,especially —CH₂—CH₂— or —CH(CH₃)—;

(19) a compound of formula (I) wherein a is 1, b is 0 and T is a directbond, —C(═N—O—A₁—R₇)—, —SiR₁₄(R₁₅)— or —C , especially —SiR₁₄(R₁₅)—;

(20) a compound of formula (I) wherein R₆ is C₁-C₄alkyl, aryl, or arylmono- to penta-substituted by substituents selected independently of oneanother from the group consisting of R₅;

R₆ being especially phenyl that is unsubstituted or mono- ordi-substituted, especially mono-substituted, by halogen, C₁-C₄alkyl,halo-C₁-C₄alkyl or by halo-C₁-C₄alkoxy, especially mono-substituted byfluorine, chlorine, C₁-C₄alkyl, trifluoromethyl or by trifluoromethoxy.

Special preference is given to the compounds of Tables 1 to 15.

The invention relates also to a process for the preparation of thecompounds of formula (I) and, where applicable, their E/Z isomers,mixtures of E/Z isomers and/or tautomers, in each case in free form orin salt form, which process comprises, for example, either

a1) reacting a compound of formula

which is known or can be prepared in accordance with methods known perse and wherein X, Y, Z, R₃, R₄ and R₉ are as defined for formula (I) andX₁ is a leaving group, preferably in the presence of a base, With acompound of formula

wherein a, b, n, A, D, G, T, L, R₂, R₅, R₆ and R₇ are as defined forformula (I) and wherein the provisos mentioned above for the compoundsof formula (I) apply, or

a2) reacting a compound of formula

wherein a, b, n, A, D, G, T, L, R₂, R₅, R₆ and R₇ are as defined forformula (I) and wherein the provisos mentioned above for the compoundsof formula (I) apply, optionally in the presence of a base, with acompound of formula

which is known or can be prepared in accordance with methods known perse and wherein X, Y, Z, R₃, R₄ and R₉ are as defined for formula (I), or

b) to prepare a compound of formula (I) wherein Y is NHR: and Z is O,reacting a compound of formula (I) wherein Y is OR₁ with a compound ofthe formula R₈NH₂, which is known or can be prepared in accordance withmethods known per se and wherein R₈ is as defined for formula (I), or

c) to prepare a compound of formula (I) wherein Y is NHR₈ and Z is S,reacting a compound of formula (I) wherein Y is R₈NH₂ and Z is O withP₄S₁₀ or Lawesson's reagent(2,4bis-(methoxyphenyl)-1,3-dithia-2,4-diphosphetane-2,4-disulfide), or

d) to prepare a compound of formula (I) wherein Z is SO, reacting acompound of formula (I) wherein Z is S with an oxidising agent,

and, in each case, if desired, converting a compound of formula (I)obtainable according to the process or by a different method, or an E/Zisomer or tautomer thereof, in each case in free form or in salt form,into a different compound of formula (I) or an E/Z isomer or tautomerthereof, in each case in free form or in salt form, separating a mixtureof E/Z isomers obtainable according to the process and isolating thedesired isomer and/or converting a free compound of formula (I)obtainable according to the process or by a different method, or an E/Zisomer or tautomer thereof, into a salt, or converting a salt of acompound of formula (I), or of an E/Z isomer or tautomer thereof,obtainable according to the process or by a different method into thefree compound of formula (I), or an E/Z isomer or tautomer thereof, orinto a different salt.

The invention relates also to a process for the preparation of compoundsof formula (III), in each case in free form or in salt form, whichprocess comprises, for example,

e) reacting a compound of formula (IV) wherein a, b, n, A, D, G, T, L,R₂, R₅, R₆ and R₇ are as defined for formula (I) and wherein theprovisos mentioned above for the compounds of formula (I) apply,optionally in the presence of a base, with H₂NOH or with a salt thereof,or

f) reacting a compound of formula

wherein a, b, n, A, D, G, T, L, R₂, R₅, R₆ and R₇ are as defined forformula (I) and wherein the provisos mentioned above for the compoundsof formula (i) apply, optionally in the presence of a base, with acompound of formula

R₇AONH₂  (VII),

which is known or can be prepared according to methods known per so andwherein A and R₇ are as defined for formula (I) and, in each case, ifdesired, converting a compound of formula (III) obtainable according tothe process or by a different method, or an E/Z isomer or tautomerthereof, in each case in free form or in salt form, into a differentcompound of formula (III) or an E/Z isomer or tautomer thereof, in eachcase in free form or in salt form, separating a mixture of E/Z isomersobtainable according to the process and isolating the desired isomerand/or converting a free compound of formula (III) obtainable accordingto the process or by a different method, or an E/Z isomer or tautomerthereof, into a salt, or converting a salt of a compound of formula(III), or of an E/Z isomer or tautomer thereof, obtainable according tothe process or by a different method into the free compound of formula(III), or an E/Z isomer or tautomer thereof, or into a different salt.

The invention relates also to a process for the preparation of acompound of formula

wherein a, b, n, D, G, T, L, R₂, R₅ and R₆ are as defined for formula(I), which process comprises

g) in the case where L in formula (VIII) is a radical

wherein R₁₈ is as defined above for formula (I), reacting a compound offormula

wherein a, n, D, G, T and R₅ are as defined for formula (I), with acompound of formula

O₂N—CH₂—R₁₈  (X),

wherein R₁₈ is as defined for formula (I), in the presence of anisocyanate, especially a phenyl isocyanate; or reacting a compound offormula (IX) with a compound of formula

HO—N═C(Hal)—C(═O)—R₁₈  (XI),

wherein R₁₈ is as defined for formula (I) and Hal is a halogen atom,preferably chlorine; or

h) when L in the compound of formula (VII) is a radical—C(═O)—C(═O)—R₁₈, oxidising a compound of formula

wherein a, n, D, G, T, R₅ and R₆ are as defined for formula (I); or

i) reacting a compound of formula

wherein b, n, L, R₂ and R₅ are as defined for formula (I) and Hal is ahalogen atom, preferably fluorine, with a compound of formula

R₆—T—(C₁-C₈alkylene)—D—H  (XIV),

wherein R₆ and T are as defined for formula (I); or

k) reacting a compound of formula

wherein b, n, D, G, R₂ and R₅ are as defined for formula (I), with acompound of formula

R₆—T—(C₁-C₈alkylene)—Hal  (XVI),

wherein R₆ and T are as defined above for formula (I) and Hal is ahalogen atom, preferably chlorine or bromine; or

l) in the case where, in a compound of formula (VIII), T is —C≡C—,reacting a compound of formula

wherein R₂, R₅, L, D, G, n and b are as defined above for formula (I),with a compound of the formula Hal—R_(6,) which is known or can beprepared in accordance with methods known per se, and wherein Hal ishalogen, preferably bromine or iodine, especially iodine, and R₁₈ is asdefined for formula (I); or

m) if L in the compound of formula (VIII) is P(O)_(v),R₁₁,R₁₂,P(S)_(w)R₁₁R₁₂ or N(aryl)R₁₃, reacting a compound of formula

which is known or can be prepared in accordance with methods known perse, and wherein a, n, D, G, T, R₂, R₅ and R₆ are as defined for formula(I) and Hal is a halogen atom, preferably bromine or iodine, with acompound of formula

H—P(O)_(v)R₁₁R₁₂ (XIX), of formula

H—P(S)_(w)R₁₁R₁₂ (XX), or of formula

H—N(aryl)R₁₃  (XXI),

which are known or can be prepared in accordance with methods known perse, and wherein v, w, R₁₁, R₁₂, R₁₃ and aryl are as defined for formula(I), preferably in the presence of a base and a catalyst, especially atransition metal catalyst, more especially a palladium catalyst or aferrocene derivative;

and, in each case, if desired, converting a compound of formula (VIII)obtainable according to the process or by a different method, or an E/Zisomer or tautomer thereof, in each case in free form or in salt form,into a different compound of formula (VIII) or an E/Z isomer or tautomerthereof, in each case in free form or in salt form, separating a mixtureof E/Z isomers obtainable according to the process and isolating thedesired isomer and/or converting a free compound of formula (VIII)obtainable according to the process or by a different method, or an E/Zisomer or tautomer thereof, into a salt, or converting a salt of acompound of formula (VIII), or of an E/Z isomer or tautomer thereof,obtainable according to the process or by a different method into thefree compound of formula (VIII), or an E/Z isomer or tautomer thereof,or into a different salt.

The other compounds of formula (VIII) are known or can be prepared inaccordance with methods known per se; for example a compound of formula(VIII) wherein T—R₆ is —C(R₁₆)═C(R₁₇)— is obtained by partialhydrogenation of a compound of formula (VIII) wherein T—R₆ is —C≡C—R₆; acompound of formula (VIII) wherein T is a direct bond is obtained bycomplete hydrogenation of a compound of formula (VIII) wherein T—R₆ is—C≡C—R₆ or —C(R₁₆)═C(R₁₇)—R₆, as described in analogous manner inExample P8-1; and a compound of formula (VIII) wherein T—R₆ is—C(═N—O—A₁—R₇)—R₆ is obtained by reacting a compound of formula (VIII)wherein T—R₆ is —C(═O)—R with a compound of formula H—N—O—A₁—R₇, R₆, R₇,A₁ and R₁₄ to R₁₇ are as defined above for formula (I) and Hal ishalogen, especially chlorine.

Further aspects of the invention are

o) a process for the preparation of compound of formula

wherein R₂, R₅, R₆, L, D, G, T, a, b and n are as defined in formula(I), in each case in free form or in salt form, which process comprisesreacting a compound of the formula (VIII) with a nitrite;

p) a process for the preparation of a compound of the formula (IV),which comprises reacting a compound of the formula (XXII) with acompound of the formula X₁—A—R₇, wherein X₁ is a leaving group such astoluenesulfonyloxy, trifluoromethanesulfonyloxy and halogen;

q) a process for the preparation of a compound of the formula (III),which comprises reacting a compound of the formula (IV) withhydroxylamine;

r) a process for the preparation of a compound of the formula

wherein R₂, R₅, R₆, L, D, G, T, a, b and n are as defined in formula(I), which comprises reacting a compound of the formula

wherein R₅, R₆, L, D, G, T, a, b and n are as defined in formula (I),with a nitroalkane;

s) a process for the preparation of a compound of the formula (VIII),which comprises reacting a compound of the formula (XXIII) with Fe/FeCl₃in the presence of an acid, preferrably hydrochloric acid.

The observations made above in respect of E/Z isomers and tautomers ofcompounds (I) apply analogously also in respect of the E/Z isomers andtautomers of starting materials mentioned hereinbefore and hereinafter.

The reactions described hereinbefore and hereinafter are carried out ina manner known per se, for example in the absence or usually in thepresence of a suitable solvent or diluent or of a mixture thereof, thereactions being carried out, as required, with cooling, at roomtemperature or with heating, for example in a temperature range fromapproximately 0° C. to the boiling temperature of the reaction medium,preferably from approximately 20° C. to approximately +120° C.,especially from 60° C. to 80° C., and, if required, in a closed vessel,under pressure, in an inert gas atmosphere and/or under anhydrousconditions. Especially advantageous reaction conditions may be found inthe Examples.

In the various reactions, the reactants may be reacted with one anotherwithout the addition of a solvent or diluent, for example in moltenform. Generally, however, the addition of an inert solvent or diluent ora mixture thereof is advantageous.

The products are isolated in accordance with customary methods, forexample by filtration, crystallisation, distillation or chromatography,or any suitable combination of those methods.

Variant a1/a2): Suitable leaving groups X₁ in the compounds of formula(II) are, for example, hydroxy, C₁-C₈alkoxy, halo-C₁-C₈alkoxy,C₁-C₈alkanoyloxy, mercapto, C₁-C₈alkylthio, halo-C₁-C₈alkylthio,C₁-C₈alkanesulfonyloxy, halo-C₁-C₈alkanesulfonyloxy, benzenesulfonyloxy,toluenesulfonyloxy and halogen, preferably toluenesulfonyloxy,trifluoromethanesulfonyloxy and halogen, especially halogen.

Suitable bases for facilitating the reaction are, for example, alkalimetal or alkaline earth metal hydroxides, hydrides, amides, alkanolates,acetates, carbonates, dialkylamides or alkylsilylamides, alkylamines,alkylenediamines, unsubstituted or N-alkylated, saturated or unsaturatedcycloalkytamines, basic heterocycles, ammonium hydroxides andcarbocyclic amines. There may be mentioned by way of example sodiumhydroxide, hydride, amide, methanolate, acetate and carbonate, potassiumtert-butanolate, hydroxide, carbonate and hydride, lithiumdiisopropylamide, potassium bis(trimethylsilyl)amide, calcium hydride,triethylamine, diisopropylethylamine, triethylenediamine,cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline,pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine,N-methylmorpholine, benzyltrimethylammonium hydroxide and1,5-diazabicyclo-[5.4.0]undec-5-ene (DBU).

Examples of solvents or diluents include: aromatic, aliphatic andalicyclic hydrocarbons and halogenated hydrocarbons, such as benzene,toluene, xylene, mesitylene, Tetralin, chlorobenzene, dichlorobenzene,bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane,trichloromethane, tetrachloromethane, dichloroethane, trichloroetheneand tetrachloroethene; esters, such as ethyl acetate; ethers, such asdiethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether,tert-butyl methyl ether, ethylene glycol monomethyl ether, ethyleneglycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethylether, tetrahydrofuran and dioxane; ketones, such as acetone, methylethyl ketone and methyl isobutyl ketone; alcohols, such as methanol,ethanol, propanol, isopropanol, butanol, ethylene glycol and glycerol;amides, such as N,N-dimethylformamide, N,N-diethylformamide,N,N-dimethylacetamide, N-methylpyrrolidone and hexamethylphosphoric acidtriamide; nitriles, such as acetonitrile and propionitrile; andsulfoxides, such as dimethyl sulfoxide. If the reaction is carried outin the presence of a base, bases used in excess, such as triethylamine,pyridine, N-methylmorpholine or N,N-diethylaniline, may also serve assolvents or diluents.

The reaction is carried out advantageously in a temperature range fromapproximately 0° C. to approximately 180° C., especially fromapproximately 10° C. to approximately 80° C., in many cases in the rangefrom room temperature to the reflux temperature of the reaction mixture.

Preference is given to a reaction duration of from approximately 0.1 toapproximately 24 hours, especially from approximately 0.5 toapproximately 2 hours.

In a preferred embodiment of variant a1/a2), a compound of formula (II)is reacted with a compound of formula (III) at from 0° C. to 80° C.,preferably from 10° C. to 30° C., in an inert solvent, preferably anamide, especially N,N-dimethylformamide, in the presence of a metalhydride, preferably sodium hydride.

Especially preferred conditions for the reaction are described inExamples P1-1 d), P1-2, P3f) and P5f).

Variant b): Examples of solvents or diluents include those mentioned invariant a1/a2).

The reaction is carried out advantageously in a temperature range fromapproximately 0° C. to approximately 180° C., especially fromapproximately 10° C. to approximately 80° C., in many cases in the rangefrom room temperature to the reflux temperature of the reaction mixture.Preference is given to a reaction duration of from approximately 0.1 toapproximately 24 hours, especially from approximately 0.5 toapproximately 2 hours.

Especially preferred conditions for the reaction are described inExamples P1-3 and P5-1 g).

Variant c): Examples of solvents or diluents include: aromatic,aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, suchas benzene, toluene, xylene, mesitylene, Tetralin, chlorobenzene,dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane,dichloromethane, trichloromethane, tetrachloromethane, dichloroethane,trichloroethene and tetrachloroethene; ethers, such as diethyl ether,dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methylether, ethylene glycol monomethyl ether, ethylene glycol monoethylether, ethylene glycol dimethyl ether, dimethoxydiethyl ether,tetrahydrofuran and dioxane; and sulfoxides, such as dimethyl sulfoxide.

The reaction is carried out advantageously in a temperature range fromapproximately 0° C. to approximately +120° C., preferably fromapproximately 80° C. to approximately +120° C.

Preference is given to a reaction duration of from approximately 0.1 toapproximately 24 hours, especially from approximately 0.5 toapproximately 2 hours.

Variant d): Suitable oxidising agents are, for example, inorganicperoxides, such as sodium perborate, or hydrogen peroxide, or organicperacids, such as perbenzoic acid or peracetic acid, or mixtures oforganic acids and hydrogen peroxide, for example acetic acid/hydrogenperoxide.

Examples of solvents or diluents include: aromatic, aliphatic andalicyclic hydrocarbons and halogenated hydrocarbons, such as benzene,toluene, xylene, mesitylene, Tetralin, chlorobenzene, dichlorobenzene,bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane,trichloromethane, tetrachloromethane, dichloroethane, trichloroetheneand tetrachloroethene; esters, such as ethyl acetate; ethers, such asdiethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether,tert-butyl methyl ether, ethylene glycol monomethyl ether, ethyleneglycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethylether, tetrahydrofuran and dioxane; ketones, such as acetone, methylethyl ketone and methyl isobutyl ketone; alcohols, such as methanol,ethanol and propanol; amides, such as N,N-dimethylformamide,N,N-diethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone andhexamethylphosphoric acid triamide; nitiles, such as acetonitrile andpropionitrile; and sulfoxides, such as dimethyl sulfoxide. If thereaction is carried out in the presence of an organic acid or peracid,acids used in excess, for example strong organic carboxylic acids, suchas unsubstituted or substituted, for example halo-substituted,C₁-C₄alkanecarboxylic acids, e.g. formic acid, acetic acid or propionicacid, may also serve as solvent or diluent.

The reaction is carried out advantageously in a temperature range fromapproximately 0° C. to approximately +120° C., preferably fromapproximately 0° C. to approximately +40° C.

Preference is given to a reaction duration of from approximately 0.1 toapproximately 24 hours, especially from approximately 0.5 toapproximately 2 hours.

Variant e): Suitable bases for facilitating the reaction are, forexample, those mentioned in variant a1/a2).

Examples of solvents or diluents include those mentioned in varianta1/a2).

The reaction is carried out advantageously in a temperature range fromapproximately 0° C. to approximately 180° C., especially fromapproximately 10° C. to approximately 80° C., in many cases in the rangefrom room temperature to the reflux temperature of the reaction mixture.

Preference is given to a reaction duration of from approximately 0.1 toapproximately 24 hours, especially from approximately 0.5 toapproximately 2 hours.

Especially preferred conditions may be found in Example P3 e).

Variant D): Suitable bases for facilitating the reaction are, forexample, those mentioned in variant a1/a2).

Examples of solvents or diluents include those mentioned in varianta1/a2).

The reaction is carried out advantageously in a temperature range fromapproximately 0° C. to approximately 180° C., especially fromapproximately 10° C. to approximately 80° C., in many cases in the rangefrom room temperature to the reflux temperature of the reaction mixture.

Preference is given to a reaction duration of from approximately 0.1 toapproximately 24 hours, especially from approximately 0.5 toapproximately 2 hours.

In a preferred embodiment of variant f), a compound of formula (VI) isreacted with a compound of formula (VII) at from 0° C. to 120° C.,preferably from 60° C. to 120° C., in an inert solvent, preferably anamine, especially pyridine. Especially preferred conditions may be foundin Example P1-1c) and also in the analogous reaction described inExample P3 e).

Especially preferred conditions for process variants g), h), i), k), l)and m) may be found in the Examples. In particular, the conditions forthe process according to variant g) may be found in Examples P9-1 andP9-2; according to variant h) in Example P6-1; according to variant i)in Example P1-la); according to variant k) in Examples P3b) and P5b);according to variant 1) in Example P7-1; and according to variant m) inExamples P101 and P12-1 or applied analogously to those processes.

Some of the compounds of formulae (I) and (III) to (XXIV) may be in theform of one of the possible isomers or in the form of a mixture thereof,for example according to the number of asymmetric carbon atoms and theabsolute and relative configuration thereof in the form of pure isomers,such as antipodes and/or diastereoisomers, or in the form of mixtures ofisomers, such as mixtures of enantiomers, for example racemates,mixtures of diastereoisomers or mixtures of racemates; the inventionrelates both to the pure isomers and to all possible mixtures of isomersand this is to be understood accordingly hereinbefore and hereinafter,even if stereochemical details are not specifically mentioned in eachcase.

Mixtures of diastereoisomers and mixtures of racemates of compounds offormulae (I) and some of the compounds (III) to (XXIV) that areobtainable in accordance with the process depending upon the startingmaterials and procedures chosen, or by other means, can be separatedinto the pure diastereoisomers or racemates in known manner on the basisof the physicochemical differences between the constituents, for exampleby fractional crystallisation, distillation and/or chromatography.

Mixtures of enantiomers, such as racemates, so obtainable can beseparated into the optical antipodes by known methods, for example byrecrystallisation from an optically active solvent, by chromatography onchiral adsorbents, for example high-pressure liquid chromatography(HPLG) on acetyl cellulose, with the aid of suitable microorganisms, bycleavage with specific immobilised enzymes, and via the formation ofinclusion compounds, for example using chiral crown ethers, in whichcase only one enantiomer is complexed.

Apart from by the separation of corresponding mixtures of isomers, it ispossible according to the invention to obtain pure diastereoisomers orenantiomers also by generally known methods of diastereoselective orenantioselective synthesis, for example by carrying out the processaccording to the invention with starting materials having appropriatestereochemistry.

It is advantageous to isolate or synthesise the biologically more activeisomer, for example enantiomer, or mixture of isomers, for examplemixture of enantiomers, insofar as the individual components havedifferent biological activity.

Some of the compounds (I) and (III) to (XXIV) can also be obtained inthe form of their hydrates and/or may include other solvents, forexample solvents that may have been used for the crystallisation ofcompounds in solid form.

The invention relates to all those embodiments of the process accordingto which a compound obtainable as starting material or intermediate atany stage of the process is used as starting material and all or some ofthe remaining steps are carried out, or a starting material is used inthe form of a derivative or a salt and/or its racemates or antipodes,or, especially, is formed under the reaction conditions.

In the process of the present invention there are preferably used thosestarting materials and intermediates which result in the compounds offormula (I) described at the beginning as being especially valuable.

The invention relates especially to the preparation processes describedin Examples P1 to P12.

The invention relates also to starting materials and intermediates usedaccording to the invention in the preparation of compounds of formula(I), especially the compounds of formulae (III), (IV), (VI), (VIII),(IX), (XII), (XIII), (XV), (XVII), (XVIII), (XXII), (XXIII) and (XXIV),which are novel, to their use and to processes for the preparationthereof. In particular, the compounds of formulae (III) and (VI) can beprepared analogously to Examples P1 c) and P1 b), respectively.

The compounds of formulae (II), (V), (VII), (X), (XI), (XIV), (XVI) and(XIX) to (XXI) are known or can be prepared in accordance with methodsknown per se.

In the area of pest control, the compounds of formula (I) according tothe invention are valuable preventive and/or curative active ingredientshaving a very advantageous biocidal spectrum even at low rates ofconcentration, while being well tolerated by warm-blooded animals, fishand plants. The compounds of the invention are effective against all orindividual development stages of normally sensitive animal pests, butalso of resistant animal pests, such as insects and representatives ofthe order Acarina, and phytopathogenic fungi. The insecticidal, ovicidaland/or acaricidal action of the compounds of the invention may manifestitself directly, i.e. in the mortality of the pests, which occursimmediately or only after some time, for example during moulting, or oftheir eggs, or indirectly, for example in reduced oviposition and/orhatching rate, good activity corresponding to a mortality of at least 50to 60%.

The mentioned animal pests include, for example, those mentioned inEuropean Patent Application EP-A-736 252. Accordingly, the said pestsmentioned in EP-A-736 252 are included by reference in the subjectmatter of the present invention.

The mentioned phytopathogenic fungi include, for example:

of the class of the Fungi imperfecti, for example, Botrytis spp.,Pyricularia spp., Helminthosporium spp., Fusarium spp., Septoria spp.,Cereo spora spp. and Altemaria spp.;

of the class of the Basidiomycetes, for example, Rhizoctonia spp.,Hemileia spp. and Puccinia spp.;

of the class of the Ascomycetes, for example, Venturia spp., Erysiphespp., Podosphaera spp., Monilinia spp. and Uncinula spp.; and

of the class of the Oomycetes, for example, Phytophthora spp., Pythiumspp. and Plasmopara spp..

With the compounds according to the invention it is possible to control,i.e. to inhibit or destroy, pests of the mentioned type occurringespecially on plants, more especially on useful plants and ornamentalsin agriculture, in horticulture and in forestry, or on parts of suchplants, such as the fruit, blossom, leaves, stems, tubers or roots,while in some cases parts of the plants that grow later are alsoprotected against those pests.

Target crops are especially cereals, such as wheat, barley, rye, oats,rice, maize and sorghum; beet, such as sugar beet and fodder beet;fruit, such as pomes, stone fruit and soft fruit, such as apples, pears,plums, peaches, almonds, cherries, or berries, for example strawberries,raspberries and blackberries; leguminous plants, such as beans, lentils,peas and soybeans; oil plants, such as rape, mustard, poppy, olives,sunflowers, coconut, castor oil plants, cocoa beans and groundnuts;cucurbitaceae, such as marrows, cucumber and melons; fibre plants, suchas cotton, flax, hemp and jute; citrus fruit, such as oranges, lemons,grapefruit and mandarins; vegetables, such as spinach, lettuce,asparagus, cabbages, carrots, onions, tomatoes, potatoes and paprika;lauraceae, such as avocados, cinnamon and camphor; and tobacco, nuts,coffee, aubergines, sugar cane, tea, pepper, vines, hops, bananas andnatural rubber plants, as well as ornamentals.

The compounds according to the invention are especially suitable forcontrolling insects and representatives of the order Acarina, especiallyplant-destructive feeding insects, such as Anthonomus grandis,Diabrotica balteata, Heliothis virescens larvae, Plutella xylostella andSpodoptera littoralis larvae, and spider mites, such as Tetranychusspp., in cotton, fruit, maize, soybean, rape and vegetable crops.

Further areas of use of the compounds according to the invention are theprotection of stored goods and stocks and materials, and also in thehygiene sector, especially the protection of domestic animals andproductive livestock against pests of the mentioned type.

The invention therefore relates also to pesticides, such as emulsifiableconcentrates, suspension concentrates, directly sprayable or dilutablesolutions, coatable pastes, dilute emulsions, wettable powders, solublepowders, dispersible powders, wettable powders, dusts, granules orencapsulations in polymer substances, comprising—at least—one of thecompounds of the invention, the type of formulation being chosen inaccordance with the intended objectives and prevailing circumstances.

The active ingredient is used in those compositions in pure form: asolid active ingredient, for example, in a specific particle size, orpreferably together with—at least—one of the adjuvants customary informulation technology, such as extenders, for example solvents or solidcarriers, or surface-active compounds (surfactants).

Formulation adjuvants used are, e.g., solid carriers, solvents,stabilisers, “slow release” adjuvants, colorants and optionallysurface-active substances (surfactants). Suitable carriers and adjuvantsinclude any substances customarily used in plant protectioncompositions, especially in compositions for controlling slugs andsnails. Suitable adjuvants, such as solvents, solid carriers,surface-active compounds, non-ionic surfactants, cationic surfactants,anionic surfactants and other adjuvants in the compositions usedaccording to the invention include, for example, the same substances asthose described in EP-A-736 252. Accordingly, the said adjuvantsmentioned in EP-A-736 252 are included by reference in the subjectmatter of the present invention.

The compositions usually comprise 0.1 to 99%, preferably 0.1 to 95%, ofactive ingredient, and 1 to 99.9%, preferably 5 to 99.9%, of—atleast—one solid or liquid adjuvant, it generally being possible for 0 to25%, preferably 0.1 to 20%, of the composition to be surfactants (ineach case percentages are by weight). Whereas commercial products willpreferably be formulated as concentrates, the end user will normallyemploy dilute formulations which have substantially lower activeingredient concentrations. Preferred formulations have especially thefollowing composition (%=percent by weight):

Emulsifiable concentrates: active ingredient:   1 to 90%, preferably 5to 20% surfactant:   1 to 30%, preferably 10 to 20% solvent:   5 to 98%,preferably 70 to 85% Dusts: active ingredient:  0.1 to 10%, preferably0.1 to 1% solid carrier:   99.9 to 90%, preferably 99.9 to 99%Suspension concentrates: active ingredient:   5 to 75%, preferably 10 to50% water:   94 to 24%, preferably 88 to 30% surfactant:   1 to 40%,preferably 2 to 30% Wettable powders: active ingredient: 0.5 to 90%,preferably 1 to 80% surfactant: 0.5 to 20%, preferably 1 to 15% solidcarrier:   5 to 99%, preferably 15 to 98% Granules: active ingredient:0.5 to 30%, preferably 3 to 15% solid carrier: 99.5 to 70%, preferably97 to 85%

The activity of the compositions according to the invention can besubstantially broadened and adapted to prevailing circumstances by theaddition of other insecticidal, acaricidal and/or fungicidal activeingredients. Examples of suitable additional active ingredients includerepresentatives of the following classes of compounds: organophosphoruscompounds, nitrophenols and derivatives, formamidines, ureas,carbamates, pyrethroids, chlorinated hydrocarbons and Bacillusthuringiensis preparations. The compositions according to the inventionmay also comprise further solid or liquid adjuvants, such asstabilisers, for example vegetable oils or epoxidised vegetable oils(e.g. epoxidised coconut oil, rape oil or soybean oil), antifoams, forexample silicone oil, preservatives, viscosity regulators, bindersand/or tackifiers, as well as fertilisers or other active ingredientsfor obtaining special effects, for example bactericides, nematicides,molluscicides or selective herbicides.

The compositions according to the invention are prepared in knownmanner, in the absence of adjuvants, for example by grinding and/orsieving a solid active ingredient or mixture of active ingredients, forexample to a specific particle size, or in the presence of at least oneadjuvant, for example by intimately mixing and/or grinding the activeingredient or mixture of active ingredients with the adjuvant(s). Theinvention relates also to those processes for the preparation of thecompositions according to the invention and to the use of the compoundsof formula (I) in the preparation of those compositions.

The invention relates also to the methods of application of thecompositions, i.e. the methods of controlling pests of the mentionedtype, such as spraying, atomising, dusting, coating, dressing,scattering or pouring, which are selected in accordance with theintended objectives and prevailing circumstances, and to the use of thecompositions for controlling pests of the mentioned type. Typical ratesof concentration are from 0.1 to 1000 ppm, preferably from 0.1 to 500ppm, of active ingredient. The rates of application per hectare aregenerally from 1 to 2000 g of active ingredient per hectare, especiallyfrom 10 to 1000 g/ha, preferably from 20 to 600 g/ha.

A preferred method of application in the area of plant protection isapplication to the foliage of the plants (foliar application), thenumber of applications and the rate of application depending on the riskof infestation by the pest in question. However, the active ingredientcan also penetrate the plants through the roots (systemic action) if thelocus of the plants is impregnated with a liquid formulation or if theactive ingredient is incorporated in solid form into the locus of theplants, for example into the soil, e.g. in granular form (soilapplication). In paddy rice crops, such granules may be applied inmetered amounts to the flooded rice field.

The compositions according to the invention are also suitable forprotecting plant propagation material, e.g. seed, such as fruit, tubersor grains, or plant cuttings, from fungal infections and animal pests.The propagation material can be treated with the formulation beforeplanting: seed, for example, can be dressed before being sown. Thecompounds of the invention can also be applied to grains (coating),either by impregnating the grains with a liquid formulation or bycoating them with a solid formulation. The formulation can also beapplied to the planting site when the propagation material is beingplanted, for example to the seed furrow during sowing. The inventionrelates also to those methods of treating plant propagation material andto the plant propagation material thus treated.

The following Examples are intended to illustrate the invention. They donot limit the invention. Temperatures are given in degrees Celsius.

PREPARATION EXAMPLES

Example P1-1:2-[[[(1-Methyl-2-(4(1-{4-chlorophenyl}-ethoxy)-phenyl)-[ethoximino]-ethylidene)amino]oxy]methyl]-α-(methoxymethylene)-phenylaceticacid methyl ester

a) 1-[4-(1-{4-Chlorophenyl}ethoxy)-phenyl]propan-1-one

26.5 g of 1-(4-chlorophenyl)-ethanol are added dropwise to 7.9 g ofsodium hydride (55% in oil) in 250 ml of dimethylacetamide and themixture is stirred at room temperature for 30 minutes. 25.7 g of4-fluoropropiophenone are then added dropwise; the mixture is heated to100° C. and stirred for 90 minutes. After cooling, the reaction mixtureis concentrated in vacua; the residue is taken up in ethyl acetate,washed twice with water and once with saturated sodium chloride solutionand dried over sodium sulfate. The solvent is evaporated off in vacuoand the residue is purified by recrystallisation from hexane to yieldthe title compound having a melting point 70-71° C.

b) 1-(4(1-{4-Chlorophenyl}-ethoxy)phenyl-1,2-propanedione-2-oxime

Dry HCl gas is introduced into 200 ml of diethyl ether over a period of0.5 minutes and 43.2 g of1-[4-(1-{4-chlorophenyl}-ethoxy)-phenyl]-propan-1-one are then added.21.0 g of isopentyl nitrite are then added dropwise and the reactionmixture is then stirred for 3 hours at room temperature. The reactionmixture is concentrated by evaporation in vacuo and the crude product ispurified by chromatography on silica gel using ethyl acetate/hexane(1:3), yielding the title compound having a melting point of 88-90° C.

c)1-[4-(1-{4-Chlorophenyl}-ethoxy)-phenyl]-1,2-propanedione-[ethyloxime]-2-oxime

A mixture of 29.0 g of1-(4-(1-{4-chlorophenyl}-ethoxy)-phenyl)-1,2-propanedione-2-oxime and9.4 g of O-ethylhydroxylamine hydrochloride in 150 ml of pyridine isboiled at reflux for 1 hour. After cooling, the reaction mixture isconcentrated by evaporation in vacuo. The residue is dissolved in ethylacetate; the organic phase is washed twice with water and once withsaturated sodium chloride solution, dried with sodium sulfate andconcentrated by evaporation. The crude product is stirred together withhexane; filtration is carried out and the filter residue is dried,yielding the title product having a melting point of 132-134° C.

d)2-[[[(1-Methyl-2-(4-(1-{4-chlorophenyl}-ethoxy)-phenyl)-[ethoxyimino]ethylidene)-amino]oxy]methyl]-α-(methoxymethylene)-phenylaceticacid methyl ester

7 g of1-[4-(1-{4-chlorophenyl)-ethoxy}-phenyl]-1,2-propanedione-[ethyloxime]-2-oximedissolved in 25 ml of N,N-dimethylformamide are added dropwise to asuspension of 0.9 g of sodium hydride (55% in oil) in 40 ml ofN,N-dimethylformamide and the reaction mixture is then stirred for 10minutes at room temperature. 5.5 g of2-(bromomethyl)-α-(methoxymethylene)-phenylacetic acid methyl ester in20 ml of N,N-dimethylformamide are then added dropwise and the reactionmixture is stirred for a further 1 hour at room temperature. The mixtureis then rendered acidic with acetic acid and concentrated by evaporationin vacuo. The residue is dissolved in ethyl acetate and the solution iswashed three times with water and once with saturated sodium chloridesolution, dried with sodium sulfate and concentrated by evaporation invacuo. Purification by flash chromatography (silica gel, ethylacetate/hexane 1:3) yields the E isomer of the title compound having amelting point of 107-109° C. (compound 1-4.2).

Example P1-2:2-[[[(1-Methyl-2-(4-(1-{4-chlorophenyl}-ethoxy)-phenyl)[ethoxyimino]ethylidene)amino]oxy]methyl]-α-(methoxyimino)-phenylacetic acid methyl ester

In a manner analogous to that described in Example P1-1 d),1-[4-(1-{4-chlorophenyl}ethoxy)-phenyl]-1,2-propanedione-[ethyloxime]-2-oximeand 2-(bromomethyl)-α-(methoxyimino)-phenylacetic acid methyl esteryield the title compound having a melting point of 111-113° C. (compound2.4-2).

Example P1-3:2-[[[(1-Methyl-2-(4-(1-{4-chlorophenyl}-ethoxy)-phenyl)-[ethoxyimino]ethylidene)amino]oxy]methyl]-α-(methoxyimino)-phenylacetic acid methylamide

A mixture of 4.0 g of2-[[[(1-methyl-2-(4-(1-{4-chlorophenyl}-ethoxy)-phenyl)-2-E-[ethoxyimino]ethylidene)amino]oxy]methyl]-α-(methoxyimino)-phenylaceticacid methyl ester and 5.3 ml of a 8M solution of methylamine in ethanolis left to stand at room temperature for 4 days. The mixture is thenconcentrated by evaporation in vacuo. The residue is taken up withmethyl acetate; the solution is washed with water and saturated sodiumchloride solution, dried over sodium sulfate and concentrated byevaporation in vacuo. The residue is recrystallised from methylacetate/hexane 1:1 to yield the title compound having a melting point of81-83° C. (compound 3-4.2).

Example P2: It is also possible to prepare the other compounds listed inTables 1.1 to 3.26 in a manner analogous to that described in ExampleP1; c.propyl denotes cyclopropyl.

TABLE A Compounds of general formula (I) wherein A-R₇ is defined asfollows Number A-R₇ A.1  CH₃ A.2  C₂H₅ A.3  n-C₃H₇ A.4  iso-C₃H₇ A.5 n-C₄H₉ A.6  n-C₆H₁₃ A.7  CH₂F A.8  CHF₂ A.9  CH₂CF₃ A.10 CH₂CH═CH₂ A.11CH₂CH═CHCH₃ A.12 CH₂CH═C(CH₃)₂ A.13 CH₂CH═CHCl A.14 CH₂CH═CCl₂ A.15CH₂C(CH₃)═CH₂ A.16 CH₂C≡CH A.17 CH₂Si(CH₃)₃ A.18 CH₂-c.propyl-2,2-Cl₂A.19 CH₂-c.propyl A.20 CH₂CN A.21 CH₂COOCH₃ A.22 CH₂COOC₂H₅ A.23CH₂COO-iso-C₃H₇ A.24 CH(CH₃)COOC₂H₅ A.25 C(═O)OC₂H₅ A.26 C(═O)NHCH₃ A.27C(═O)C(═O)OC₂H₅ A.28 CH₂C₆H₅ A.29 CH₂C₆H₄-2-F A.30 CH₂C₆H₄-3-F A.31CH₂C₆H₄-4-F A.32 CH₂C₆H₄-2-Cl A.33 CH₂C₆H₄-3-Cl A.34 CH₂C₆H₄-4-Cl A.35CH₂C₆H₄-2-Br A.36 CH₂C₆H₄-3-Br A.37 CH₂C₆H₄-4-Br A.38 CH₂C₆H₄-2-CF₃ A.39CH₂C₆H₄-3-CF₃ A.40 CH₂C₆H₄-4-CF₃

Table 1-1: Compounds of general formula

TABLE 1-1 Compounds of general formual (I.1)

wherein (R₅)_(S) is 4-CF₃ and the substituent A—R₇ corresponds in eachcase to a line of Table A.

Table 1-2: Compounds of general formula (I.1) wherein (R₅)_(S) is 3-CF₃and the substituent A—R₇ corresponds in each case to a line of Table A.

Table 1-3: Compounds of general formula (I.1) wherein (R₅)_(S) is 2-CF₃and the substituent A—R₇ corresponds in each case to a line of Table A.

Table 1-4: Compounds of general formula (I.1) wherein (R₅)_(S) is 4-Cland the substituent A—R₇ corresponds in each case to a line of Table A.

Table 1-5: Compounds of general formula (I.1) wherein (R₅)_(S) is 3-Cland the substituent A—R₇ corresponds in each case to a line of Table A.

Table 1-6: Compounds of general formula (I.1) wherein (R₅)_(S) is 2-Cland the substituent A—R₇ corresponds in each case to a line of Table A.

Table 1-7: Compounds of general formula (I.1) wherein (R₅)_(S) is 4-Brand the substituent A—R₇ corresponds in each case to a line of Table A.

Table 1-8: Compounds of general formula (I.1) wherein (R₅)_(S) is 3-Brand the substituent A—R₇ corresponds in each case to a line of Table A.

Table 1-9: Compounds of general formula (I.1) wherein (R₅)_(S) is 2-Brand the substituent A—R₇ corresponds in each case to a line of Table A.

Table 1-10: Compounds of general formula (I.1) wherein (R₅)_(S) is 4-Fand the substituent A—R₇ corresponds in each case to a line of Table A.

Table 1-11: Compounds of general formula (I.1) wherein (R₅)_(S) is 3-Fand the substituent A—R₇ corresponds in each case to a line of Table A.

Table 1-12: Compounds of general formula (I.1) wherein (R₅)_(S) is 2-Fand the substituent A—R₇ corresponds in each case to a line of Table A.

Table 1-13: Compounds of general formula (I.1) wherein (R₅)_(S) is2,4-Cl₂ and the substituent A—R₇ corresponds in each case to a line ofTable A.

Table 1-14: Compounds of general formula (I.1) wherein (R₅)_(S) is3,4-C₆ and the substituent A—R₇ corresponds in each case to a line ofTable A.

Table 1-15: Compounds of general formula (I.1) wherein (R₅)_(S) is4-O—CF₃ and the substituent A—R₇ corresponds in each case to a line ofTable A.

Table 1-16: Compounds of general formula (I.1) wherein (R₅)_(S) is 4-CH₃and the substituent A—R₇ corresponds in each case to a line of Table A.

Table 1-17: Compounds of general formula (I.1) wherein (R₅)_(S) is4-C₂H₅ and the substituent A—R₇ corresponds in each case to a line ofTable A.

Table 1-18: Compounds of general formula (I.1) wherein (R₅)_(S) is4-n-C₃H₇ and the substituent A—R₇ corresponds in each case to a line ofTable A.

Table 1-19: Compounds of general formula (I.1) wherein (R₅)_(S) is4-iso-C₃H₇ and the substituent A—R₇ corresponds in each case to a lineof Table A.

Table 1-20: Compounds of general formula (I.1) wherein (R₅)_(S) is4-n-C₄H₉ and the substituent A—R₇ corresponds in each case to a line ofTable A.

Table 1-21: Compounds of general formula (I.1) wherein (R₅)_(S) is4-isobutyl and the substituent A—R₇ corresponds in each case to a lineof Table A.

Table 1-22: Compounds of general formula (I.1) wherein (R₅)_(S) is4-sec-butyl and the substituent A—R₇ corresponds in each case to a lineof Table A.

Table 1-23: Compounds of general formula (I.1) wherein (R₅)_(S) is4-tert-butyl and the substituent A—R₇ corresponds in each case to a lineof Table A.

Table 1-24: Compounds of general formula (I.1) wherein (R₅)_(s) is 4-CNand the substituent A—R₇ corresponds in each case to a line of Table A.

Table 1-25: Compounds of general formula (I.1) wherein (R₅)_(S) is4-O—CH₃ and the substituent A—R₇ corresponds in each case to a line ofTable A.

Table 1-26: Compounds of general formula (I.1) wherein (R₅)_(S) is2,4-F₂ and the substituent A—R₇ corresponds in each case to a line ofTable A.

Compound of formula (I.1) wherein A—R₇ is ethyl and (R₅)_(S) is4-chlorine: m.p.: 107-109° C. (compound 1-4.2).

TABLE 2-1 Compounds of general formula (I.2)

wherein (R₅)_(S) is 4-CF₃ and the substituent A—R₇ corresponds in eachcase to a line of Table A.

Table 2-2: Compounds of general formula (I.2) wherein (R₅)_(S) is 3-CF₃and the substituent A—R₇ corresponds in each case to a line of Table A.

Table 2-3: Compounds of general formula (I.2) wherein (R₅)_(S) is 2-CF₃and the substituent A—R₇ corresponds in each case to a line of Table A.

Table 2-4: Compounds of general formula (I.2) wherein (R₅)_(S) is 4-Cland the substituent A—R₇ corresponds in each case to a line of Table A.

Table 2-5: Compounds of general formula (I.2) wherein (R₅)_(S) is 3-Cland the substituent A—R₇ corresponds in each case to a line of Table A.

Table 2-6: Compounds of general formula (I.2) wherein (R₅)_(S) is 2-Cland the substituent A—R₇ corresponds in each case to a line of Table A.

Table 2-7: Compounds of general formula (I.2) wherein (R₅)_(S) is 4-Brand the substituent A—R₇ corresponds in each case to a line of Table A.

Table 28: Compounds of general formula (I.2) wherein (R₅)_(S) is 3-Brand the substituent A—R₇ corresponds in each case to a line of Table A.

Table 2-9: Compounds of general formula (I.2) wherein (R₅)_(S) is 2-Brand the substituent A—R₇ corresponds in each case to a line of Table A.

Table 2-10: Compounds of general formula (I.2) wherein (R₅)_(S) is 4-Fand the substituent A—R₇ corresponds in each case to a line of Table A.

Table 2-11: Compounds of general formula (I.2) wherein (R₅)_(S) is 3-Fand the substituent A—R₇ corresponds in each case to a line of Table A.

Table 2-12: Compounds of general formula (I.2) wherein (R₅)_(S) is 2-Fand the substituent A—R₇ corresponds in each case to a line of Table A.

Table 2-13: Compounds of general formula (I.2) wherein (R₅)_(S) is2,4-Cl₂ and the substituent A—R₇ corresponds in each case to a line ofTable A.

Table 2-14: Compounds of general formula (I.2) wherein (R₅)_(S) is3,4-Cl₂ and the substituent A—R₇ corresponds in each case to a line ofTable A.

Table 2-15: Compounds of general formula (I.2) wherein (R₅)_(S) is4-O—CF₃ and the substituent A—R₇ corresponds in each case to a line ofTable A.

Table 2-16: Compounds of general formula (I.2) wherein (R₅)_(S) is 4-CH₃and the substituent A—R₇ corresponds in each case to a line of Table A.

Table 2-17: Compounds of general formula (I.2) wherein (R₅)_(S) is4-C₂H₅ and the substituent A—R₇ corresponds in each case to a line ofTable A.

Table 2-18: Compounds of general formula (I.2) wherein (R₅)_(S) is4-n-C₃H₇ and the substituent A—R₇ corresponds in each case to a line ofTable A.

Table 2-19: Compounds of general formula (I.2) wherein (R₅)_(S) is4-iso-C₃H₇ and the substituent A—R₇ corresponds in each case to a lineof Table A.

Table 2-20: Compounds of general formula (I.2) wherein (R₅)_(S) is4-n-C₄H₉ and the substituent A—R₇ corresponds in each case to a line ofTable A.

Table 2-21: Compounds of general formula (I.2) wherein (R₅)_(S) is4-isobutyl and the substituent A—R₇ corresponds in each case to a lineof Table A.

Table 2-22: Compounds of general formula (I.2) wherein (R₅)_(S) is4-sec-butyl and the substituent A—R₇ corresponds in each case to a lineof Table A.

Table 2-23: Compounds of general formula (I.2) wherein (R₅)_(S) is4-tert-butyl and the substituent A—R₇ corresponds in each case to a lineof Table A.

Table 2-24: Compounds of general formula (I.2) wherein (R₅)_(S) is 4-CNand the substituent A—R₇ corresponds in each case to a line of Table k

Table 2-25: Compounds of general formula (I.2) wherein (R₅)_(S) is4-O—CH₃ and the substituent A—R₇ corresponds in each case to a line ofTable A.

Table 2-26: Compounds of general formula (I.2) wherein (R₅)_(S) is2,4-F₂ and the substituent A—R₇ corresponds in each case to a line ofTable A.

Compound of formula (I.2) wherein A—R₇ is ethyl and (R₅)_(S) is4-chlorine: m.p.: 111-113° C. (compound 2-4.2).

Table 3-1: Compounds of general formula

TABLE 3-1 Compounds of general formula (I.3)

wherein (R₅)_(S) is 4-CF₃ and the substituent A—R₇ corresponds in eachcase to a line of Table A.

Table 3-2: Compounds of general formula (I.3) wherein (R₅)_(S) is 3-CF₃and the substituent A—R₇ corresponds in each case to a line of Table A.

Table 3-3: Compounds of general formula (I.3) wherein (R₅)_(S) is 2-CF₃and the substituent A—R₇ corresponds in each case to a line of Table A.

Table 3-4: Compounds of general formula (I.3) wherein (R₅)_(S) is 4-Cland the substituent A—R₇ corresponds in each case to a line of Table A.

Table 3-5: Compounds of general formula (I.3) wherein (R₅)_(S) is 3-Cland the substituent A—R₇ corresponds in each case to a line of Table A.

Table 3-6: Compounds of general formula (I.3) wherein (R₅)_(S) is 2-Cland the substituent A—R₇ corresponds in each case to a line of Table A.

Table 3-7: Compounds of general formula (I.3) wherein (R₅)_(S) is 4-Brand the substituent A—R₇ corresponds in each case to a line of Table A.

Table 3-8: Compounds of general formula (I.3) wherein (R₅)_(S) is 3-Brand the substituent A—R₇ corresponds in each case to a line of Table A.

Table 3-9: Compounds of general formula (I.3) wherein (R₅)_(S) is 2-Brand the substituent A—R₇ corresponds in each case to a line of Table A.

Table 3-10: Compounds of general formula (I.3) wherein (R₅)_(S) is 4-Fand the substituent A—R₇ corresponds in each case to a line of Table A.

Table 3-11: Compounds of general formula (I.3) wherein (R₅)_(S) is 3-Fand the substituent A—R₇ corresponds in each case to a line of Table A.

Table 3-12: Compounds of general formula (I.3) wherein (R₅)_(S) is 2-Fand the substituent A—R₇ corresponds in each case to a line of Table A.

Table 3-13: Compounds of general formula (I.3) wherein (R₅)_(S) is2,4-Cl and the substituent A—R₇ corresponds in each case to a line ofTable A.

Table 3-14: Compounds of general formula (I.3) wherein (R₆)_(S) is3,4-Cl₂ and the substituent A—R₇ corresponds in each case to a line ofTable A.

Table 3-15: Compounds of general formula (I.3) wherein (R₅)_(S) is4-O—CF₃ and the substituent A—R₇ corresponds in each case to a line ofTable A.

Table 3-16: Compounds of general formula (I.3) wherein (R₅)_(S) is 4-CH₃and the substituent A—R₇ corresponds in each case to a fine of Table A.

Table 3-17: Compounds of general formula (I.3) wherein (R₅)_(S) is4-C₂H₅ and the substituent A—R₇ corresponds in each case to a line ofTable A.

Table 3-18: Compounds of general formula (I.3) wherein (R₅)_(S) is4-n-C₃H₇ and the substituent A—R₇ corresponds in each case to a line ofTable A.

Table 3-19: Compounds of general formula (I.3) wherein (R₅)_(S) is4iso-C₃H₇ and the substituent A—R₇ corresponds in each case to a line ofTable A

Table 3-20: Compounds of general formula (I.3) wherein (R₅)_(S) is4-n-C₄H₉ and the substituent A—R₇ corresponds in each case to a line ofTable A.

Table 3-21: Compounds of general formula (I.3) wherein (R₅)_(S) is4-isobutyl and the substituent A—R₇ corresponds in each case to a lineof Table A.

Table 3-22: Compounds of general formula (I.3) wherein (R₅)_(S) is4-sec-butyl and the substituent A—R₇ corresponds in each case to a lineof Table A.

Table 3-23: Compounds of general formula (I.3) wherein (R₅)_(S) is4-tert-butyl and the substituent A—R₇ corresponds in each case to a lineof Table A.

Table 324: Compounds of general formula (I.3) wherein (R₅)_(S) is 4-CNand the substituent A—R₇ corresponds in each case to a line of Table A.

Table 3-25: Compounds of general formula (I.3) wherein (R₅)_(S) is4-O—CH₃ and the substituent A—R₇ corresponds in each case to a line ofTable A.

Table 3-26: Compounds of general formula (I.3) wherein (R₅)_(S) is2,4-F₂ and the substituent A—R₇ corresponds in each case to a line ofTable A.

Compound of formula (I.3) wherein A—R₇ is ethyl and (R₅)_(S) is4-chlorine: m.p.: 81-83° C. (compound 3-4.2).

Compounds of Formula

The figures given in the column “Phys. data” denote melting points in °C.

X Y AR₇ R R₅ Phys. data CH O—CH₃ CH₃ CH₃ 4-Cl 128-130 CH O—CH₃ CH₃ CH₃4-CF₃ 116-118 CH O—CH₃ CH₂CH₃ CH₃ 4-CF₃  98-100 CH O—CH₃ CH₃ CH₂CH₃ 4-Cl105-107 CH O—CH₃ CH₂CH₃ CH₂CH₃ 4-F resin CH O—CH₃ CH₂CH₃ CH₂CH₃ 4-Cl89-91 CH O—CH₃ CH₃ CH₂CH₃ 4-F 101-103 CH O—CH₃ CH₃ CH₂CH₃ 4-tert-butyl101-102 CH O—CH₃ CH₃ CH₂CH₃ 4-CF₃ 124-126 CH O—CH₃ CH₂CH₃ CH₂CH₃ 4-CF₃112-114 N O—CH₃ CH₃ CH₃ 4-Cl 121-123 N O—CH₃ CH₃ CH₃ 4-CF₃ 116-118 NO—CH₃ CH₂CH₃ CH₃ 4-CF₃ 112-114 N O—CH₃ CH₃ CH₂CH₃ 4-Cl 100-102 N O—CH₃CH₂CH₃ CH₂CH₃ 4-F 102-104 N O—CH₃ CH₂CH₃ CH₂CH₃ 4-Cl 103-105 N O—CH₃ CH₃CH₂CH₃ 4-F 116-118 N O—CH₃ CH₂CH₃ CH₂CH₃ 4-tert-butyl resin N O—CH₃ CH₃CH₂CH₃ 4-tert-butyl 106-107 N O—CH₃ CH₃ CH₂CH₃ 4-CF₃ 114-116 N O—CH₃CH₂CH₃ CH₂CH₃ 4-CF₃ 72-74 N NHCH₃ CH₃ CH₃ 4-Cl 146-148 N NHCH₃ CH₃ CH₃4-CF₃ 130-132 N NHCH₃ CH₂CH₃ CH₃ 4-CF₃ 148-150 N NHCH₃ CH₃ CH₂CH₃ 4-Cl139-141 N NHCH₃ CH₂CH₃ CH₂CH₃ 4-F 112-114 N NHCH₃ CH₂CH₃ CH₂CH₃ 4-Cl131-133 N NHCH₃ CH₃ CH₂CH₃ 4-F 124-126 N NHCH₃ CH₃ CH₂CH₃ 4-CF₃ 149-151N NHCH₃ CH₂CH₃ CH₂CH₃ 4-CF₃ 134-136

Example P3: Preparation of2-[2-(2-{4-[2-(4-chlorophenyl-2-methoxyimino-ethoxy]-phenyl}-2-ethoxyimino-1-methyl-ethylideneaminooxymethyl)-phenyl]-3-methoxy-acrylicacid methyl ester of the formula

a) 4-Chlorophenacyl bromide O-methyloxime

50.3 g of 4-chlorophenacyl bromide in 300 ml of glacial acetic acid arestirred with 23 g of sodium acetate and 21.6 g O-methylhydroxylaminehydrochloride for 2 hours at 70° C. 150 ml of ethyl acetate are added tothe mixture, which is then extracted by washing several times with waterand saturated sodium chloride solution. The organic phase is dried oversodium sulfate and concentrated by evaporation in vacuo. Crystallisationfrom hexane yields 4-chlorophenacyl bromide O-methyloxime having amelting point of 57 to 60° C.

b) Compound of the formula

19.7 g of 1-(4-hydroxyphenyl)-propan-2-one, 34.4 g of 4-chlorophenacylbromide O-methyloxime and 36 g of potassium carbonate are stirred in 200ml of dimethylformamide for 2 hours at 80° C. 200 ml of ethyl acetateare added to the reaction mixture, which is then washed several timeswith water and saturated sodium chloride solution, dried over sodiumsulfate and concentrated by evaporation in vacuo. The crude product ischromatographed on silica gel using tert-butyl methyl ether/hexane(1:19) to yield the title compound in the form of an oil.

c) Compound of the formula

35 g of a compound obtainable according to process P3b) are placed in200 ml of methanol and 18 ml of isopentyl nitrite. At 0° C., 30 ml of a30% solution of sodium methanolate in methanol are added dropwise andthe mixture is stirred for 2 hours at room temperature. The solvent isevaporated off, and 200 ml of ethyl acetate and 200 ml of water areadded; the aqueous phase is separated off and the organic phase is thenwashed several times with water. Evaporating off the solvent andrecrystallisation of the residue from dichloromethane/hexane yield thetitle product having a melting point of 131-133° C.

d)1-{4-[2-(4-Chlorophenyl)-2-methoxyimino-ethoxy]-phenyl}-propane-1,2-dione1-(O-ethyloxime) of the formula

16.7 g of a compound obtainable according to process P3c) are stirredtogether with 5 ml of ethyl bromide and 10 g of potassium carbonate in150 ml of dimethylformamide for 2 hours at room temperature. 300 ml ofdiethyl ether are added to the reaction mixture, which is then washedseveral times with water and saturated sodium chloride solution and theether phase is concentrated to dryness by evaporation. Recrystallisationof the residue from diethyl ether/hexane yields the title product havinga melting point of 76-81° C.

e)1-{4-[2-(4-Chlorophenyl)-2-methoxyimino-ethoxy]-phenyl}-propane-1,2-dione1-(O-ethyloxime) 2-oxime of the formula

14.5 g of a compound obtainable according to process P3d) are stirredtogether with 3.1 g of hydroxylammonium chloride in 50 ml of pyridinefor a period of 2 hours at 70° C. The reaction mixture is concentratedand 200 ml of ethyl acetate are added; the mixture is washed severaltimes with water and saturated sodium chloride solution and the organicphase is concentrated to dryness by evaporation. Recrystallisation ofthe residue from dichloromethane/hexane yields the title product havinga melting point of 136-137° C.

f)2-[2-(2-{4-[2-(4-Chlorophenyl)-2-methoxyimino-ethoxy]-phenyl}-2-ethoxyimino-1-methylethylideneaminooxymethyl)-phenyl]-3-methoxy-acrylicacid methyl ester

2.9 g of a compound obtainable according to process P3e) in 30 ml ofdimethylformamide are combined with 0.34 g of sodium hydride under anargon atmosphere. After evolution of hydrogen has ceased, 2 g of2-(bromomethyl)-(methoxymethylene)-phenylacetic acid methyl ester areadded and the mixture is stirred for one hour at room temperature. Themixture is rendered acidic with acetic acid and 150 ml of ethyl acetateare added; the mixture is washed several times with water and saturatedsodium chloride solution and dried over sodium sulfate; the solvent isevaporated off. Chromatography of the residue on silica gel usingtert-butyl methyl ether/hexane (1:9) yields the title compound in theform of a resin (compound 4-1.7).

Example P4: It is also possible to prepare the other compounds listed inTable 4 in a manner analogous to that described in Example P3. Thefigures given in the column “Phys. data” denote melting points in ° C.

TABLE 4-1 Compounds of general formula (I.4.1)

Compd. X Y AR₇ R₅ Phys. data 4-1.1 CH OCH₃ CH₂CH₃ 4-F resin 4-1.2 NO—CH₃ CH₂CH₃ 4-F resin 4-1.3 N NH—CH₃ CH₂CH₃ 4-F  87-89 4-1.4 CH OCH₃CH₃ 4-F foam 4-1.5 N O—CH₃ CH₃ 4-F resin 4-1.6 N NH—CH₃ CH₃ 4-F 106-1084-1.7 CH OCH₃ CH₂CH₃ 4-Cl resin 4-1.8 N O—CH₃ CH₂CH₃ 4-Cl resin 4-1.9 NNH—CH₃ CH₂CH₃ 4-Cl 108-111 4-1.10 CH OCH₃ CH₃ 4-Cl resin 4-1.11 N O—CH₃CH₃ 4-Cl resin 4-1.12 N NH—CH₃ CH₃ 4-Cl 104-107 4-1.13 CH OCH₃ CH₂CH₃4-CF₃ oil 4-1.14 N O—CH₃ CH₂CH₃ 4-CF₃ 106-109 4-1.15 N NH—CH₃ CH₂CH₃4-CF₃ 116-118 4-1.16 CH OCH₃ CH₃ 4-CF₃ resin 4-1.17 N O—CH₃ CH₃ 4-CF₃resin 4-1.18 N NH—CH₃ CH₃ 4-CF₃ 126-129 4-1.19 CH OCH₃ CH₂CH₃ H resin4-1.20 N O—CH₃ CH₂CH₃ H resin 4-1.21 N NH—CH₃ CH₂CH₃ H 124-126 4-1.22 CHOCH₃ CH₃ H resin 4-1.23 N O—CH₃ CH₃ H resin 4-1.24 N NH—CH₃ CH₃ H116-119 4-1.25 CH OCH₃ CH₃ 4-CH₃ resin 4-1.26 N O—CH₃ CH₃ 4-CH₃ resin4-1.27 N NH—CH₃ CH₃ 4-CH₃  92-96 4-1.28 CH OCH₃ CH₂CH₃ 4-CH₃ resin4-1.29 N O—CH₃ CH₂CH₃ 4-CH₃ resin 4-1.30 N NH—CH₃ CH₂CH₃ 4-CH₃ 117-1194-1.31 CH OCH₃ CH₂—C≡CH 4-CH₃ resin 4-1.32 N O—CH₃ CH₂—C≡CH 4-CH₃ resin4-1.33 N NH—CH₃ CH₂—C≡CH 4-CH₃ 103-105

TABLE 4-2 Compounds of formula (I.4.2)

Phys. No. X Y R₆ AR₇ A₁R₇₇ data 4-2.1 CH OCH₃ CH₃ C₂H₅ CH₃ oil 4-2.2 NOCH₃ CH₃ C₂H₅ CH₃ oil 4-2.3 N NHCH₃ CH₃ C₂H₅ CH₃ 121-123 4-2.4 CH OCH₃p-tolyl CH₃ benzyl 123-125 4-2.5 N OCH₃ p-tolyl CH₃ benzyl resin 4-2.6 NNHCH₃ p-tolyl CH₃ benzyl 129-132 4-2.7 CH OCH₃ CH₃ C₂H₅ benzyl oil 4-2.8N OCH₃ CH₃ C₂H₅ benzyl oil 4-2.9 N NHCH₃ CH₃ C₂H₅ benzyl resin 4-2.10 CHOCH₃ CH₃ CH₃ benzyl oil 4-2.11 N OCH₃ CH₃ CH₃ benzyl oil 4-2.12 N NHCH₃CH₃ CH₃ benzyl  83-85 4-2.13 CH OCH₃ CH₃ CH₂C≡CH benzyl oil 4-2.14 NOCH₃ CH₃ CH₂C≡CH benzyl oil 4-2.15 N NHCH₃ CH₃ CH₂C≡CH benzyl resin4-2.16 N OCH₃ CH₃ C₂H₅ 4-CF₃- oil benzyl

Example P5-1:2-[[[(1-Methyl-2-(4-[{dimethyl-(4-fluorophenyl)-silyl}methoxy]phenyl)-[ethoxyimino]ethylidene)amino]oxy]methyl]-α-(methoxyimino)-phenylaceticacid methyl ester and2-[[[(1-methyl-2-(4-[{dimethyl-(4-fluorophenyl)-silyl}methoxy]phenyl)-[ethoxyimino]ethyidene)amino]oxy]methyl]-α-(methoxyimino)-phenylacetic acid methylamide

a) Chloromethyl-dimethyl-(4-fluorophenyl)-silane

250 ml of n-butyl lithium (1.6M in hexane) are added to 39 ml of4-bromo-fluoro-benzene in 400 ml of tetrahydrofuran within a period of45 minutes with stirring at −70° C. The mixture is stirred for a further30 minutes and then 53 ml of chloromethyl-dimethyl-chlorosilanedissolved in 50 ml of tetrahydrofuran are added dropwise. The mixture isstirred at −70° C. for a further 30 minutes and the temperature of thereaction mixture is then allowed to rise to 0° C. The reaction mixtureis poured onto 200 ml of ice, and 300 ml of diethyl ether are added; themixture is washed with water and saturated sodium chloride solution anddried over sodium sulfate; the solvent is evaporated off in vacuo.Distillation of the residue at 97-105° C. (21 mbar) yields the titleproduct.

b) 1-(4-[{Dimethyl-(4-fluorophenyl)-silyl}methoxy]phenyl)-propan-2-one

30 g of 1-(4-hydroxyphenyl)-propan-2-one and 45.5 g ofchloromethyl-dimethyl-(4-fluorophenyl)-silane in 400 ml of dimethylsulfoxide are stirred with 42 g of potassium carbonate and 2 g ofpotassium iodide for 12 hours at 70° C. The reaction mixture is pouredinto 1.6 liters of ice water and 500 ml of diethyl ether are added; theether phase is extracted by washing several times with water andsaturated sodium chloride solution and dried over sodium sulfate; thesolvent is evaporated off. Distillation at 150° C. (0.01 mbar) yieldsthe title product.

c)1-(4-[{Dimethyl-(4-fluorophenyl)-silyl}methoxy]phenyl)propane-1,2-dione-1-oxime

28 ml of a 30% solution of sodium methanolate in methanol are added atroom temperature to 31.6 g of1-(4-[{dimethyl-(4-fluorophenyl)-silyl}methoxy]phenyl)-propan-2-one in300 ml of methanol, and 27 ml of isopentyl nitrite are then addeddropwise. The reaction mixture is stirred for a further hour andrendered neutral with acetic acid; the solvent is evaporated off invacuo. 200 ml of ethyl acetate are added to the residue; the organicphase is washed with water and saturated sodium chloride solution anddried over sodium sulfate; the solvent is evaporated off in vacuo.Recrystallisation from diethyl ether/hexane yields the title producthaving a melting point of 115-117° C.

d)1-(4-[{Dimethyl-(4-fluorophenyl)silyl}methoxy]phenyl)propane-1,2-dione-1-ethyloxime

13.8 g of1-(4-[{dimethyl-(4-fluorophenyl)-silyl}methoxy]phenyl)-propane-1,2-dione-1-oxime,4 ml of ethyl bromide and 9 g of potassium carbonate are stirred in 150ml of dimethylformamide for 2 hours at room temperature. 200 ml ofdiethyl ether are added to the reaction mixture, which is then washedwith water and saturated sodium chloride solution; the organic phase isdried and the solvent is evaporated off to yield the title product inthe form of an oil.

e)1-(4-[{Dimethyl-(4-fluorophenyl)-silyl}methoxy]phenyl)-propane-1,2-dione-1-ethyloxime-2-oxime

14.3 g of1-(4-[{dimethyl-(4-fluorophenyl)-silyl}methoxy]phenyl)-propane-1,2-dione-1-ethyl-oximein 50 ml of pyridine are stirred with 3.5 g of hydroxylammonium chloridefor 2 hours at 70° C. The reaction mixture is concentrated in vacuo andethyl acetate is added to the residue; the organic phase is washed withwater and saturated sodium chloride solution and dried over sodiumsulfate; the solvent is evaporated off. Recrystallisation from hexaneyields the title product having a melting point of 100-102° C.

f)2-[[[(1-Methyl-2-(4-[{dimethyl-(4-fluorophenyl)-silyl}methoxy]phenyl)-[ethoimino]-ethylidene)amino]oxy]methyl]-α-(methoxyimino)-phenylacetic acid methyl ester 3.9 gof1-(4-[{dimethyl-(4-fluorophenyl)-silyl}methoxy]phenyl-propane-1,2-dione-1-ethyloxime-2-oximeare added at room temperature to 0.31 g of sodium hydride in 60 ml ofdimethylformamide. After evolution of hydrogen has ceased, 2.9 g of2-(bromomethyl)-α-(methoxyimino)-phenylacetic acid methyl ester areadded and stirring is carried out for 1 hour at room temperature. Themixture is rendered neutral with acetic acid and 100 ml of ethyl acetateare added; the mixture is washed with water and saturated sodiumchloride solution and dried over sodium sulfate; the solvent isevaporated off. Chromatography on silica gel using tert-butyl methylether/hexane (1:3) yields the title product in the form of an oil(compound 5.22).

g)2-[[[(1-Methyl-2-(4-[{dimethyl-(4-fluorophenyl)-silyl}methoxy]phenyl)-[ethoxyimino]-ethylidene)amino]oxy]methyl]-α-(methoxyimino)-phenylaceticacid methylamide

3 ml of a 8M solution of methylamine in ethanol are added to 2.9 g of2-[[[(1-methyl-2-(4-[{dimethyl-(4-fluorophenyl)-silyl}methoxy]phenyl)-[ethoxyimino]ethylidene)amino]oxy]-methyl]-α-(methoxyimino)-phenylacetic acid methyl ester in 30ml of methanol and stirring is carried out for 2 days at roomtemperature. The reaction mixture is concentrated to dryness byevaporation. Recrystallisation of the residue from hexane yields thetitle compound having a melting point of 88-90° C. (compound 5.23).

Example P5-2: It is also possible to prepare the other compounds listedin Table 5 in a manner analogous to that described in Example P51. Thefigures given in the column “Phys. data” denote melting points in ° C.

TABLE 5 Compounds of general formula Compd. X Y AR₇ R₅ Phys. data 5.1 CHOCH₃ CH₃ H oil 5.2 N OCH₃ CH₃ H oil 5.3 N NH—CH₃ CH₃ H 128-130 5.4 CHOCH₃ CH₂CH₃ H oil 5.5 N OCH₃ CH₂CH₃ H oil 5.6 N NH—CH₃ CH₂CH₃ H oil 5.7CH OCH₃ CH₂CH₃ 3-CF₃ oil 5.8 N OCH₃ CH₂CH₃ 3-CF₃ oil 5.9 CH OCH₃ CH₃3-CF₃ oil 5.10 N OCH₃ CH₃ 3-CF₃ oil 5.11 N NH—CH₃ CH₃ 3-CF₃ resin 5.12CH OCH₃ CH₂CH₃ 4-CF₃ resin 5.13 N OCH₃ CH₂CH₃ 4-CF₃ 85-87 5.14 N NH—CH₃CH₂CH₃ 4-CF₃ 129-131 5.15 CH OCH₃ CH₂CH₃ 4-Cl oil 5.16 N OCH₃ CH₂CH₃4-Cl oil 5.17 N NH—CH₃ CH₂CH₃ 4-Cl 108-110 5.18 CH OCH₃ CH₃ 4-Cl oil5.19 N OCH₃ CH₃ 4-Cl oil 5.20 N NH—CH₃ CH₃ 4-Cl  99-101 5.21 CH OCH₃CH₂CH₃ 4-F resin 5.22 N OCH₃ CH₂CH₃ 4-F resin 5.23 N NH—CH₃ CH₂CH₃ 4-F88-90 5.24 CH OCH₃ CH₃ 4-F 101-103 5.25 N OCH₃ CH₃ 4-F 75-77 5.26 NNH—CH₃ CH₃ 4-F 100-102 5.27 CH OCH₃ CH₂CH₃ 2-F oil 5.28 N OCH₃ CH₂CH₃2-F oil 5.29 N NH—CH₃ CH₂CH₃ 2-F 75-79 5.30 CH OCH₃ CH₂CH₃ 2-CH₃ oil5.31 N OCH₃ CH₂CH₃ 2-CH₃ 77-80 5.32 N NH—CH₃ CH₂CH₃ 2-CH₃ 125-127 5.33CH OCH₃ CH₃ 2-CH₃ oil 5.34 N OCH₃ CH₃ 2-CH₃ oil 5.35 N NH—CH₃ CH₃ 2-CH₃81-84 5.36 CH OCH₃ CH₂—C≡CH 2-CH₃ resin 5.37 N OCH₃ CH₂—C≡CH 2-CH₃ 85-875.38 N NH—CH₃ CH₂—C≡CH 2-CH₃  99-102 5.39 CH OCH₃ CH₃ 3-CH₃ 5.40 N OCH₃CH₂CH₃ 3-F 5.41 N NH—CH₃ CH₃ 3-F 5.42 CH OCH₃ CH₃ 3-OCF₃ 5.43 N OCH₃ CH₃4-O—CF₃ 5.44 N NH—CH₃ CH₃ 2-OCF₃ 5.45 CH OCH₃ CH₂CH₃ 3-OCF₃ 5.46 N OCH₃CH₂CH₃ 4-O—CF₃ 5.47 N NH—CH₃ CH₂CH₃ 2-OCF₃

Example P6-1:2-[[[(1-Methyl-2-(4-{2-(3-methylphenyl)-ethanedione}-phenyl)-[methoxyimino]ethylidene)amino]oxy]methyl]-α-(methoxyimino)-phenylaceticacid methylamide

2.2 g of2-[[[(1-methyl-2-(4-(3-methylphenyl-ethynyl)-phenyl)-2-E-[ethoxyimino]ethylidene)amino]oxy]methyl]-α-(methoxyimino)-phenylaceticacid methylamide in 12 ml of dimethyl sulfoxide are stirred with 0.7 gof iodine for a period of 6 hours at 150° C. After cooling, the reactionmixture is purified on silica gel using ether/hexane (3:1), yielding thetitle compound in the form of a resin (compound 6.3).

Example P6-2: It is also possible to prepare the other compounds listedin Table 6 in a manner analogous to that described in Example P6-1. Thefigures given in the column “Phys. data” denote melting points in ° C.

TABLE 6 Compounds of general formula (I.6)

Compd. X Y AR₇ R₅ Phys. data 6.1 CH OCH₃ CH₃ 2-CH₃ 6.2 N O—CH₃ CH₃ 4-CH₃6.3 N NH—CH₃ CH₃ 3-CH₃ resin 6.4 CH OCH₃ CH₂CH₃ 2-Cl 6.5 N O—CH₃ CH₂CH₃4-Cl 6.6 N NH—CH₃ CH₂CH₃ 3-Cl 6.7 CH OCH₃ CH₂CH₃ 2-F 6.8 N O—CH₃ CH₂CH₃4-F 6.9 CH OCH₃ CH₃ 3-F 6.10 N O—CH₃ CH₃ 2-CF₃ 6.11 N NH—CH₃ CH₃ 4-CF₃6.12 CH OCH₃ CH₂CH₃ 3-CF₃ 6.13 N O—CH₃ CH₂CH₃ 2-OCF₃ 6.14 N NH—CH₃CH₂CH₃ 4-OCF₃ 6.15 CH OCH₃ CH₂CH₃ 3-OCF₃

Example P7-1:2-[[[(1-Methyl-2-(4-{3-(3-trifluoromethylphenyl)-prop-2-yn-1-yl-oxy}-phenyl)-[methoxyimino]ethylidene)amino]oxy]methyl]-α-(methoxymethylene)-phenylaceticacid methyl ester

1.5 ml of 3-iodobenzotrifluoride and 0.1 g ofbis(triphenylphosphine)palladium(II) chloride are added to a solution of2.2 g of2-[[[(1-methyl-2-({4-propargyloxy}-phenyl)-[methoxyimino]ethylidene)amino]oxy]methyl]-α-(methoxymethylene)-phenylaceticacid methyl ester in 100 ml of triethylamine and 40 ml oftetrahydrofuran. The mixture is stirred for 3 hours at 60° C. andfiltered, and the filtrate is concentrated by evaporation. The residueis purified on silica gel using ethyl acetate/hexane (1:2) to yield thetitle compound in the form of a resin (compound 7.10).

Example P7-2: It is also possible to prepare the other compounds listedin Table 7 in a manner analogous to that described in Example P7-1. Thefigures given in the column “Phys. data” denote melting points in ° C.

TABLE 7 Compounds of general formula (I.7)

Compd. X Y AR₇ R₅ Phys. data 7.1 CH OCH₃ CH₃ 2-CH₃ 7.2 N O—CH₃ CH₃ 4-CH₃7.3 N NH—CH₃ CH₃ 3-CH₃ 7.4 CH OCH₃ CH₂CH₃ 2-Cl 7.5 N O—CH₃ CH₂CH₃ 4-Cl7.6 N NH—CH₃ CH₂CH₃ 3-Cl 7.7 CH OCH₃ CH₂CH₃ 2-F 7.8 N O—CH₃ CH₂CH₃ 4-F7.9 CH OCH₃ CH₃ 3-F 7.10 CH O—CH₃ CH₃ 3-CF₃ resin 7.11 N NH—CH₃ CH₃4-CF₃ 7.12 CH OCH₃ CH₂CH₃ 2-CF₃ 7.13 N O—CH₃ CH₂CH₃ 2-OCF₃ 7.14 N NH—CH₃CH₂CH₃ 4-OCF₃ 7.15 CH OCH₃ CH₂CH₃ 3-OCF₃

Example P8-1:2-[[[(1-Methyl-2-(4-{3-(3-trifluoromethylphenyl)-n-propyl-oxy}-phenyl)-[methoxyimino]ethylidene)amino]oxy]methyl]-α-(methoxymethylene)-phenylaceticacid methyl ester

100 mg of palladium on carbon (5% Pd) are added to 1.8 g of2-[[[(1-methyl-2-(4-{3-(3-trifluoromethylphenyl)-propyn-2-yl-oxy}-phenyl-[methoxyimino]ethylidene)amino]oxy]-methyl]-α-(methoxymethylene)-phenylaceticacid methyl ester in 30 ml of tetrahydrofuran. Hydrogen is introduced atnormal pressure until one equivalent has been used. The reaction mixtureis then filtered and the filtrate is concentrated to dryness byevaporation. The residue is purified on silica gel using ethylacetate/hexane (1:2) to yield the title compound in the form of an oil(compound 8.10).

Example P8-2: It is also possible to prepare the other compounds listedin Table 8 in a manner analogous to that described in Example P8-1.

TABLE 8 Compounds of general formula (I.8)

Compd. X Y AR₇ R₅ Phys. data 8.1 CH OCH₃ CH₃ 2-CH₃ 8.2 N O—CH₃ CH₃ 4-CH₃8.3 N NH—CH₃ CH₃ 3-CH₃ 8.4 CH OCH₃ CH₂CH₃ 2-Cl 8.5 N O—CH₃ CH₂CH₃ 4-Cl8.6 N NH—CH₃ CH₂CH₃ 3-Cl 8.7 CH OCH₃ CH₂CH₃ 2-F 8.8 N O—CH₃ CH₂CH₃ 4-F8.9 CH OCH₃ CH₃ 3-F 8.10 CH O—CH₃ CH₃ 3-CF₃ oil 8.11 N NH—CH₃ CH₃ 4-CF₃8.12 CH OCH₃ CH₂CH₃ 2-CF₃ 8.13 N O—CH₃ CH₂CH₃ 2-OCF₃ 8.14 N NH—CH₃CH₂CH₃ 4-COF₃ 8.15 CH OCH₃ CH₂CH₃ 3-OCF₃

Example P9-1: Compound of the formula

1.1 g of phenyl isocyanate, 0.45 ml of nitioethane and 0.5 ml oftriethylamine are added to 2.1 g of2-[[[(1-methyl-2-(4-ethynyl-phenyl)-[methoxyimino]ethylidene)amino]oxy]methyl]-α-(methoxymethylene)-phenylaceticacid methyl ester in 40 ml of toluene. Stirring is carried out for aperiod of 5 hours at 80° C., the reaction mixture is filtered and thefiltrate is concentrated by evaporation. Purification on silica gelusing ethyl acetate/hexane 1:2 yields the title product having a meltingpoint of 116-118° C. (compound 9-1.1).

Example P9-2: Preparation of the compound of formula

1.8 g of the compound of formula

and 2 ml of triethylamine are added to 1.2 g of2-[[[(1-methyl-2-(4-ethynyl-phenyl)-[methoxyimino]ethylidene)amino]oxy]methyl]-α-(methoxyimino)-phenylaceticacid methyl ester in toluene. Stirring is carried out for 4 hours at 65°C., the reaction mixture is filtered and the filtrate is concentrated byevaporation. Purification on silica gel using toluene/diisopropylether/hexane (1:1:2) yields the title compound having a melting point of127-129° C. (compound 9-2.2).

Example P9-3: It is also possible to prepare the other compounds listedin Tables 9-1 and 9-2 in a manner analogous to that described inExamples P9-1 and P9-2. The figures given in the column “Phys. data”denote melting points in ° C.

TABLE 9-1 Compounds of general formula (I.9-1)

Compd. X Y AR₇ R₁₈ Phys. data 9-1.1 CH OCH₃ CH₃ CH₃ 116-118° C. 9-1.2 NO—CH₃ CH₃ CH₃ 9-1.3 N NH—CH₃ CH₃ CH₃ 9-1.4 CH OCH₃ CH₂CH₃ CH₃ 9-1.5 NO—CH₃ CH₂CH₃ CH₃ 9-1.6 N NH—CH₃ CH₂CH₃ CH₃ 9-1.7 CH OCH₃ CH₂CH₃ CH₂CH₃9-1.8 N O—CH₃ CH₂CH₃ CH₂CH₃ 9-1.9 CH OCH₃ CH₃ CH₂CH₃ 9-1.10 CH O—CH₃ CH₃CH₂CH₃ 9-1.11 N NH—CH₃ CH₃ —C₆H₅ 9-1.12 CH OCH₃ CH₃ —C₆H₅ 9-1.13 N O—CH₃CH₃ —C₆H₅ 9-1.14 N O—CH₃ CH₂CH₃ —C₆H₅ 9-1.15 N NH—CH₃ CH₂CH₃ —C₆H₅9-1.16 CH OCH₃ CH₂CH₃ —C₆H₅ 9-1.17 N NH—CH₃ CH₃ —C₆H₄-3-CF₃ 9-1.18 CHOCH₃ CH₃ —C₆H₄-4-CF₃ 9-1.19 N O—CH₃ CH₃ —C₆H₄-3-Cl 9-1.20 N O—CH₃ CH₂CH₃—C₆H₄-4-Cl 9-1.21 N NH—CH₃ CH₂CH₃ —C₆H₄-3-F 9-1.22 CH OCH₃ CH₂CH₃—C₆H₄-4-F

TABLE 9-2 Compounds of general formula (I.9-2)

Compd. X Y AR₇ R₅ Phys. data 9-2.1. CH OCH₃ CH₃ H 9-2.2. N O—CH₃ CH₃ H127-129 9-2.3. N NH—CH₃ CH₃ H 9-2.4. CH OCH₃ CH₂CH₃ H 9-2.5. N O—CH₃CH₂CH₃ H 9-2.6. N NH—CH₃ CH₂CH₃ H 9-2.7. CH OCH₃ CH₃ 4-Cl 9-2.8. N O—CH₃CH₃ 3-Cl 9-2.9. N NH—CH₃ CH₃ 2-Cl 9-2.10. CH OCH₃ CH₂CH₃ 4-CF₃ 9-2.11. NO—CH₃ CH₂CH₃ 3-CF₃ 9-2.12. N NH—CH₃ CH₂CH₃ 2-CF₃ 9-2.13. CH OCH₃ CH₃ 4-F9-2.14. N O—CH₃ CH₃ 3-F 9-2.15. N NH—CH₃ CH₃ 2-F 9-2.16. CH OCH₃ CH₂CH₃4-OCF₃ 9-2.17. N O—CH₃ CH₂CH₃ 3-OCF₃ 9-2.18. N NH—CH₃ CH₂CH₃ 2-OCF₃

Example P9-4: Preparation of6-chloro-3-(4′-(1-ethoxyimino-2-hydroxyimino)propyl)benzisoxazole of theformula

a) 4-Bromo-2′,4′-dichlorobenzophenone oxime:

Hydroxylammonium chloride (6.4 g) and pyridine (7.2 g) are added at roomtemperature to a solution of 4-bromo-2′,4′-dichlorobenzophenone (15.1 g)in ethanol (75 ml). After being boiled for 10 hours under reflux, thereaction mixture is concentrated by evaporation using a rotaryevaporator, and water and ethyl acetate are added to the residue. Afterwashing the organic phase and evaporating the solution, a residue isobtained which is dissolved in hexane at 30° C. and left to stand at 5°C. The solid that forms is filtered off with suction and dried in air,thereby yielding the title compound having a melting point of 125-126°C.

b) 3-(4′-Bromophenyl)-6-chlorobenzisoxazole:

20 ml of dimethylformamide are added to 10.4 g of the compoundobtainable according to a). At 30-35° C. , KOH (5.63 g) is added inportions. The mixture is then stirred at 45° C. for 1 hour and then afurther 0.94 g portion of KOH is added at 30° C. and the mixture isstirred for a further 1 hour at 45° C. to complete the reaction.Methanol (30 ml) and, after 10 minutes' stirring, water (120 ml) areadded to the reaction mixture. After cooling to −5° C., the solid formedis filtered off and dried in air to yield the title compound having amelting point of 126-127° C.

c) 4-(6′-Chlorobenzoxazol-3′-yl)benzaldehyde:

A solution of 3-(4′-bromophenyl)-6-chlorobenzoxazole (43.2 g) intetrahydrofuran (470 ml) is cooled to −70° C. under argon. Within aperiod of one hour, an approx. 1.6M n-butyl lithium solution in hexane(100 ml) is added dropwise. After 1 hour at −70° C., the reactionmixture is brought to −45° C. and a solution of N-formylpiperidine (17.5g) in tetrahydrofuran (145 ml) is added within a period of 30 minutes.The temperature is then allowed to rise to room temperature and themixture is stirred for two hours. 2N hydrochloric acid (280 ml) is addedand the mixture is stirred for a further 2 hours at room temperature.The reaction mixture is taken up in methylene chloride and washed withsaturated NaHCO₃ solution and saturated NaCl solution. After evaporatingoff the solvent, the residue is stirred together with 200 ml of diethylether. Filtration yields the title compound having a melting point of159-160° C.

d) 6Chloro-3-(4′-(2-nitropropenyl)phenyl)benzisoxazole

Ammonium acetate (12.0 g) is added to4-(6′-chlorobenzoxazol-3′-yl)benzaldehyde (35.2 g) and nitroethane (160ml). The mixture is then stirred for 4 hours under reflux. The reactionmixture is cooled to approx. 60° C. and at that temperature concentratedby evaporation in vacuo. The residue is taken up in ethyl acetate andwashed with brine. Drying over Na₂SO₄ and evaporating off solvent at 50°C. yields a residue, which is stirred together with tert-butyl methylether. The solid product obtained is filtered off with suction and driedin air, yielding the title compound having a melting point of 160-162°C.

e) 6-Chloro-3-(4′-(2-oxopropyl)phenyl)benzisoxazole

Alcohol (30 ml) and water (29 ml) are added to6-chloro+4′-(2-nitropropenyl)phenyl)benzisoxazole (18.2 g), irongranules (11.3 g) and iron(ill) chloride (0.18 g) and the mixture isheated to 70° C. with stirring. Once the temperature has reached 70° C.,20 ml of concentrated hydrochloric acid are added dropwise in such amanner that the reaction temperature can be maintained at 70° C. Afterthe addition is complete, the batch is stirred at 70° C. for 90 minutes,a further 10 ml of concentrated hydrochloric acid are added dropwise andthe stirring is continued for a further 2 hours. The reaction mixture iscooled, filtered over silica gel and diluted with ethyl acetate; theorganic phase is extracted by shaking with water and saturated NaClsolution. After drying over MgSO₄ and evaporating off the solvent, asticky residue is obtained, which is purified by means of columnchromatography (ethyl acetate/hexane 1:5), yielding the title compoundhaving a melting point of 109-110° C.

f) 6-Chloro-3-(4′-(1-hydroxyimino-2-oxo)propyl)benzisoxazole

Isopentyl nitrite (3.0 g) is slowly added dropwise at 20° C. to 7.2 g of6-chloro-3-(4′-(2-oxo-propyl)phenyl)benzisoxazole in methanol (37 ml).After the addition of 30% sodium methanolate (5.7 g), stirring iscarried out overnight at room temperature. The reaction mixture isconcentrated by evaporation at 50° C.; the residue is dissolved in waterand rendered acidic with 10% hydrochloric acid at 10° C. Ethyl acetateis added, the water phase separated and the organic phase washed withwater. Drying over MgSO₄ and concentration by evaporation yield a solid,which is stirred together with hexane, filtered off with suction anddried in air to yield the title compound having a melting point of224-226° C.

g) 6-Chloro-3-(4′-(1-ethoxyimino-2-oxo)propyl)benzisoxazole

Ethyl iodide (5.45 g) is added to6chloror(4-(1-hydroxyimino-2-oxo)propyl)benzisoxazole (7.01 g),acetonitrile (44 ml) and potassium carbonate (4.3 g). The batch isheated for 3 hours under reflux, cooled to room temperature andfiltered, the filter being rinsed with acetonitrile. The filtrate isconcentrated by evaporation using a rotary evaporator; the residue istaken up in ethyl acetate and washed with water and brine. Drying of theorganic phase over Na₂SO₄ and concentration by evaporation yield thetitle compound having a melting point of 106-107° C.

h) 6-Chloro-3-(4′-(1-ethoxymino-2-hydroxymino)propyl)benzisoxazole

Pyridine (3.6 g) is added to6-chloro-3-(4′-(1-ethoxyimino-2-oxo)propyl)benzisoxazole (7.20 g),ethanol (37 ml) and hydroxylammonium chloride (3.2 g). The batch isboiled under reflux for 2 hours. The reaction mixture is evaporated; theresidue is washed with water, taken up in ethyl acetate and then washedwith water. After drying of the organic phase over Mg₂SO₄ andconcentration using a rotary evaporator, the residue is stirred whencold together with a little diethyl ether. The resulting solid productis filtered off with suction and dried in air to yield the titlecompound having a melting point of 218-21 9° C.

Starting from the compounds according to Examples P9-4/g) and P9-4/h),compounds 9-3.1 to 9-3.3 can be prepared analogously to the processvariants a1), a2) and b).

Example P9-5: It is also possible to prepare the intermediates requiredfor the other compounds listed in Table 9-3 in a manner analogous tothat described in Example P9-4. The figures given in the column “Phys.data” denote melting points in ° C.

TABLE 9-3 Compounds of the formula

Compd. X Y AR₇ R₅ Phys. data 9-3.1 CH OCH₃ CH₂CH₃ 6-Cl 105-110 9-3.2 NO—CH₃ CH₂CH₃ 6-Cl 128-130 9-3.3 N NH—CH₃ CH₂CH₃ 6-Cl 124-126 9-3.4 CHOCH₃ CH₂CH₃ 6-Cl 9-3.5 N O—CH₃ CH₂CH₃ 6-Cl 9-3.6 N NH—CH₃ CH₂CH₃ 6-Cl9-3.7 CH OCH₃ CH₂CH₃ 5-Cl 9-3.8 N O—CH₃ CH₂CH₃ 5-Cl 9-3.9 N NH—CH₃CH₂CH₃ 5-Cl 9-3.10 CH OCH₃ CH₂CH₃ 5,6-Cl₂ 9-3.11 N O—CH₃ CH₂CH₃ 5,6-Cl₂9-3.12 N NH—CH₃ CH₂CH₃ 5,6-Cl₂ 9-3.13 CH OCH₃ CH₂CH₃ 6-CF₃ 9-3.14 NO—CH₃ CH₂CH₃ 6-CF₃ 9-3.15 N NH—CH₃ CH₂CH₃ 6-CF₃ 9-3.16 CH OCH₃ CH₂CH₃6-OCF₃ 9-3.17 N O—CH₃ CH₂CH₃ 6-OCF₃ 9-3.18 N NH—CH₃ CH₂CH₃ 6-OCF₃

Example P10-1: Preparation of

0.95 g of2-{2-[2-(4-bromophenyl)-2-methoxyimino-1-methyl-ethylideneaminooxymethyl]-phenyl}-3-methoxy-acrylicacid methyl ester, 0.4 g of triethylamine, 0.25 g oftetrakistriphenylphosphine-palladium(O), 3 ml of toluene and 0.28 g ofdiethyl phosphite are stirred under argon for 2 hours at 90° C. Thereaction mixture is taken up in ethyl acetate, washed with water, driedand concentrated. Chromatography of the crude product on silica gelusing ethyl acetatelhexane (1:1) yields 0.93 g of product having amelting point of 125-126° C. (compound 10-1.16).

Example P11: It is also possible to prepare the other compounds listedin Tables 10 and 11 in a manner analogous to that described in ExampleP10-1.

TABLE B Compounds of general formula (I.10)

No. X Y R₁₁ R₁₂ (W)_(w) B.1 CH OCH₃ C₆H₅ C₆H₅ O B.2 N OCH₃ C₆H₅ C₆H₅ OB.3 N NHCH₃ C₆H₅ C₆H₅ O B.4 CH OCH₃ 4-Cl—C₆H₅ 4-Cl—C₆H₅ O B.5 N OCH₃4-Cl—C₆H₅ 3-Cl—C₆H₅ O B.6 N NHCH₃ 4-Cl—C₆H₅ 2-Cl—C₆H₅ O B.7 CH OCH₃2,4-Cl₂—C₆H₅ 2,4-Cl₂—C₆H₅ O B.8 N OCH₃ 2,4-Cl₂—C₆H₅ 3,4-Cl₂—C₆H₅ O B.9 NNHCH₃ 2,4-Cl₂—C₆H₅ 2,5-Cl₂—C₆H₅ O B.10 CH OCH₃ 3-CF₃—C₆H₅ 3-CF₃—C₆H₅ OB.11 N OCH₃ 4-CF₃—C₆H₅ 4-CF₃—C₆H₅ O B.12 CH OCH₃ C₆H₅O C₆H₅O O B.13 NOCH₃ C₆H₅O C₆H₅O O B.14 CH OCH₃ 3,5-Cl₂—C₆H₅O 3,5-Cl₂—C₆H₅O O B.15 CHOCH₃ CH₃O CH₃O O B.16 CH OCH₃ CH₃CH₂O CH₃CH₂O O B.17 N NHCH₃ CH₃O CH₃O OB.18 CH OCH₃ 4-Cl—C₆H₅O 4-Cl—C₆H₅O O B.19 N NHCH₃ 3,5-Cl₂—C₆H₅O3,5-Cl₂—C₆H₅O O B.20 CH OCH₃ 4-Cl—C₆H₅S 4-Cl—C₆H₅S O B.21 N NHCH₃4-Br—C₆H₅S 4-Br—C₆H₅S O B.22 N OCH₃ CH₃CH₂S CH₃CH₂S S B.23 CH OCH₃4-Cl—C₆H₅S 4-Cl—C₆H₅S S B.24 N OCH₃ 4-Cl—C₆H₅S 3,5-Cl₂—C₆H₅O S B.25 NNHCH₃ CH₃CH₂S 4-Cl—C₆H₅S S B.26 CH OCH₃ CH₃CH₂O 4-Cl—C₆H₅S S B.27 N OCH₃CH₃CH₂O 4-Cl—C₆H₅S S B.28 N OCH₃ 4-CF₃—C₆H₅ CH₃CH₂S O B.29 N NHCH₃4-CF₃—C₆H₅ CH₃CH₂S O B.30 CH OCH₃ 4-CF₃—C₆H₅ CH₃S S B.31 N NHCH₃4-CF₃—C₆H₅ CH₃S S B.32 CH OCH₃ 4-Br—C₆H₅S CH₃CH₂O O B.33 N OCH₃4-Cl—C₆H₅S 3,5-Cl₂—C₆H₅O O B.34 CH OCH₃ CH₃CH₂S CH₃CH₂S w = 0 B.35 NOCH₃ 4-Cl—C₆H₅S 4-Cl—C₆H₅S w = 0 B.36 CH OCH₃ 4-Cl—C₆H₅S 3,5-Cl₂—C₆H₅O w= 0 B.37 N OCH₃ 4-Cl-C₆H₅S 3,5-Cl₂—C₆H₅O w = 0 B.38 N OCH₃ CH₃CH₂O4-Cl—C₆H₅S w = 0 B.39 CH OCH₃ C₆H₅O C₆H₅O w = 0 B.40 N NHCH₃ C₆H₅O C₆H₅Ow = 0 B.41 CH OCH₃ 4-CF₃—C₆H₅ CH₃S w = 0 B.42 N NHCH₃ 4-CF₃—C₆H₅ CH₃S w= 0

Table 10-1: Compounds of general formula (1.10) wherein AR₇ is CH₃ andthe combination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for eachcompound corresponds to a line of Table B.

Compound of formula I.10 wherein A—R₇ is methyl and the substituents X,Y, (W)_(w), R₁₁ and R₁₂ correspond to line B.1 of Table B; m.p.:103-104° C. (compound 10-1.1).

Compound of formula I.10 wherein A—R₇ is methyl and the substituents X,Y, (W)_(w), R₁₁ and R₁₂ correspond to line B.12 of Table B; m.p.: 95-96°C. (compound 10-1.12).

Table 10-2: Compounds of formula (I.10) wherein AR₇ is CH₂CH₃ and thecombination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for each compoundcorresponds to a line of Table B.

Table 10-3: Compounds of formula (I.10) wherein AR₇ is CH₂CH═CH₂ and thecombination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for each compoundcorresponds to a line of Table B.

Table 10-4: Compounds of formula (I.10) wherein AR₇ is CH₂C≡CH and thecombination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for each compoundcorresponds to a line of Table B.

Table 10-5: Compounds of formula (I.10) wherein AR₇ is CH₂CH₂CH₃ and thecombination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for each compoundcorresponds to a line of Table B.

Table 10-6: Compounds of formula (I.10) wherein ARE is CH(CH₃)₂ and thecombination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for each compoundcorresponds to a line of Table B.

Table 10-7: Compounds of formula (I.10) wherein AR₇ is CH₂CH₂CH₂CH₃ andthe combination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for eachcompound corresponds to a line of Table B.

Table 10-8: Compounds of formula (I.10) wherein AR₇ is CH(CH₃)(CH₂CH₃)and the combination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for eachcompound corresponds to a line of Table B.

Table 10-9: Compounds of formula (I.10) wherein AR₇ is C(CH₃)₃ and thecombination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for each compoundcorresponds to a line of Table B.

Table 10-10: Compounds of formula (I.10) wherein AR₇ is CH₂CF₃ and thecombination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for each compoundcorresponds to a line of Table B.

Table 10-11: Compounds of formula (I.10) wherein AR₇ is CH₂CH═C(CH₃)₂and the combination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for eachcompound corresponds to a line of Table B.

Table 10-12: Compounds of formula (I.10) wherein AR₇ is CH₂CH═CCl₂andthe combination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for eachcompound corresponds to a line of Table B.

Table 10-13: Compounds of formula (I.10) wherein AR₇ is CH₂Si(CH₃)₃ andthe combination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for eachcompound corresponds to a line of Table B.

Table 10-14: Compounds of formula (I.10) wherein AR₇ isCH₂c.propyl-2,2-Cl₂ and the combination of substituents X, Y, (W)_(w),R₁₁ and R₁₂ for each compound corresponds to a line of Table B.

Table 10-15: Compounds of formula (I.10) wherein AR₇ is CH₂CN and thecombination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for each compoundcorresponds to a line of Table B.

Table 10-16: Compounds of formula (I.10) wherein AR₇ is CH₂COOCH₃ andthe combination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for eachcompound corresponds to a line of Table B.

Table 10-17: Compounds of formula (I.10) wherein AR₇ is CH₂COO-iso-C₃H₇and the combination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for eachcompound corresponds to a line of Table B.

Table 10-18: Compounds of formula (I.10) wherein AR₇ is C(═O)OC₂H₅ andthe combination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for eachcompound corresponds to a line of Table B.

Table 10-19: Compounds of formula (I.10) wherein AR₇ is C(═O)NHCH₃ andthe combination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for eachcompound corresponds to a line of Table B.

Table 10-20: Compounds of formula (I.10) wherein AR₇ is C(═O)C(═O)OC₂H₅and the combination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for eachcompound corresponds to a line of Table B.

Table 10-21: Compounds of formula (I.10) wherein AR₇ is CH₂C₆H₅ and thecombination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for each compoundcorresponds to a line of Table B.

Table 10-22: Compounds of formula (I.10) wherein AR₇ is CH₂C₆H₄-2-F andthe combination of substituents X, Y and (W)_(w), R₁₁ and R₁₂ for eachcompound corresponds to a line of Table B.

Table 10-23: Compounds of formula (I.10) wherein AR₇ is CH₂C₆H₄-3-Cl andthe combination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for eachcompound corresponds to a line of Table B.

Table 10-24: Compounds of formula (I.10) wherein AR₇ is CH₂C₆H₄-4-Br andthe combination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for eachcompound corresponds to a line of Table B.

Table 10-25: Compounds of formula (I.10) wherein AR₇ is CH₂C₆H₄-3-CF₃and the combination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for eachcompound corresponds to a line of Table B.

Table 10-26: Compounds of formula (I.10) wherein AR₇ is CH₂CrH₄-4-CF₃and the combination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for eachcompound corresponds to a line of Table B.

TABLE 11-1 Compounds of formula (I.11)

wherein AR₇ is CH₃ and the combination of substituents X, Y, (W)_(w),R₁₁ and R₁₂ for each compound corresponds to a line of Table B.

Table 11-2: Compounds of formula (I.11) wherein AR₇ is CH₂CH₃ and thecombination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for each compoundcorresponds to a line of Table B.

Table 11-3: Compounds of formula (I.11) wherein AR₇ is CH₂CH═CH₂ and thecombination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for each compoundcorresponds to a line of Table B.

Table 114: Compounds of formula (I.11) wherein AR₇ is CH₂CCH and thecombination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for each compoundcorresponds to a line of Table B.

Table 1 1-5: Compounds of formula (I.11) wherein AR₇ is CH₂CH₂CH₃ andthe combination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for eachcompound corresponds to a line of Table B.

Table 11-6: Compounds of formula (I.11) wherein AR₇ is CH(CH₃)₂ and thecombination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for each compoundcorresponds to a line of Table B.

Table 11-7: Compounds of formula (I.11) wherein AR₇ is CH₂CH₂CH₂CH₃ andthe combination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for eachcompound corresponds to a line of Table B.

Table 11-8: Compounds of formula (I.11) wherein AR₇ is CH(CH₃)(CH₂CH₃)and the combination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for eachcompound corresponds to a line of Table B.

Table 11-9: Compounds of formula (I.11) wherein AR₇ is C(CH₃)₃ and thecombination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for each compoundcorresponds to a line of Table B.

Table 11-10: Compounds of formula (I.11) wherein AR₇ is CH₂CF₃ and thecombination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for each compoundcorresponds to a line of Table B.

Table 11-11: Compounds of formula (I.11 ) wherein AR₇ is CH₂CH═C(CH₃)₂and the combination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for eachcompound corresponds to a line of Table B.

Table 11-12: Compounds of formula (I.11) wherein AR₇ is CH₂CH═CC₁₂ andthe combination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for eachcompound corresponds to a line of Table B.

Table 11-13: Compounds of formula (I.11) wherein AR₇ is CH₂Si(CH₃)₃ andthe combination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for eachcompound corresponds to a line of Table B.

Table 11-14: Compounds of formula (I.11) wherein AR₇ isCH₂-c.propyl-2,2-Cl₂ and the combination of substituents X, Y, (W)_(w),R₁₁ and R₁₂ for each compound corresponds to a line of Table B.

Table 11-15: Compounds of formula (I.11) wherein AR₇ is CH₂CN and thecombination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for each compoundcorresponds to a line of Table B.

Table 11-16: Compounds of formula (I.11) wherein AR₇ is CH₂COOCH₃ andthe combination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for eachcompound corresponds to a line of Table B.

Table 11-17: Compounds of formula (I.11) wherein AR₇ is CH₂COO-iso-C₃H₇and the combination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for eachcompound corresponds to a line of Table B.

Table 11-18: Compounds of formula (I.11) wherein AR₇ is C(═O)OC₂H₅ andthe combination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for eachcompound corresponds to a line of Table B.

Table 11-19: Compounds of formula (I.11) wherein AR₇ is C(═O)NHCH₃ andthe combination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for eachcompound corresponds to a line of Table B.

Table 11-20: Compounds of formula (I.11) wherein AR₇ is C(═O)C(═O)OC₂H₅and the combination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for eachcompound corresponds to a line of Table B.

Table 11-21: Compounds of formula (I.11) wherein AR₇ is CH₂C₆H₅ and thecombination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for each compoundcorresponds to a line of Table B.

Table 11-22: Compounds of formula (I.11) wherein AR₇ is CH₂C₆H₄-2-F andthe combination of substituents X, Y, and (W)_(w), R₁₁ and R₁₂ for eachcompound corresponds to a line of Table B.

Table 11-23: Compounds of formula (I.11) wherein AR₇ is CH₂C₆H₄-4-Br andthe combination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for eachcompound corresponds to a line of Table B.

Table 11-24: Compounds of formula (I.11) wherein AR₇ is CH₂C₆H₄-3-CF₃and the combination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for eachcompound corresponds to a line of Table B.

Table 11-25: Compounds of formula (I.11) wherein AR₇ is CH₂C₆H₄-4-CF₃and the combination of substituents X, Y, (W)_(w), R₁₁ and R₁₂ for eachcompound corresponds to a line of Table B.

Example P12-1: Preparation of the compounds of the formula

2.4 g of 2-{2-[2-(4-bromophenyl)₂-methoxyimino-methyl-ethylideneaminooxymethyl]-phenyl}-3-methoxy-acrylic acid methylester, 0.7 g of sodium tert-butanolate, 0.25 g oftris(dibenzylacetone)dipalladium(O), 110 mg of1,1-bis(diphenylphosphine)ferrocene, 40 ml of toluene and 0.77 g of4-chloroaniline are stirred under an argon atmosphere for 4 hours at 70°C. The reaction mixture is taken up in diethyl ether, washed with brine,dried and concentrated. Chromatography of the crude product on silicagel using ethyl acetate/hexane (1:19) yields 0.8 g of the crude producthaving a melting point of 82-83° C. (compound 12-1.3).

Example P1 2-2: Preparation of the compound of formula

0.55 g of sodium hydride (55%) is added in portions to 3.5 g of3-(4-(3-fluoromethylphenylamino)phenyl-2-hydroximino-3-methoximinopropanein 40 ml of dimethylformamide under an argon atmosphere in an ice bath.After one hour, 3.4 g of 2-(α-bromo-o-tolyl)-2-methoxyimino-acetic acidmethyl ester are added and stirring is carried out for a further 20hours at room temperature. 0.6 g of acetic acid is then added and thereaction mixture is concentrated. The residue is taken up in ethylacetate; the mixture is washed with water, dried and concentrated.Chromatography of the residue on silica gel using ethyl acetate/hexane(1:9) yields 3.6 g of2-{2-[2-(4-(3-fluoromethylphenylamino)-phenyl)-2-ethoxyimino-1-methyl-ethylideneaminooxymethyl]-phenyl}-3-methoxy-acrylicacid methyl ester having a melting point of 119-120° C. (compound12-1.69).

Example P12-3: Preparation of the compound of the formula

0.2 g of2-{2-[2-(4-(4-chlorophenylamino)-phenyl)-2-methoxyimino-1-methyl-ethylideneaminooxymethyl]-phenyl}-3-methoxy-acrylicacid methyl ester and 7 ml of a 1M solution of formylacetic acidanhydride in diethyl ether are stirred under argon for 12 hours at 25°C. The reaction mixture is concentrated. Chromatography of the residueon silica gel using ethyl acetate/hexane (1:5) yields 0.03 g of thetitle product having a melting point of 145-146° C. (compound 12-1.64).

Example P12-4: It is also possible to prepare the other compounds listedin Tables 12 and 13 in a manner analogous to that described in ExamplesP1 2-1 to P12-3.

TABLE C Compounds of general formulae (I.12)

(I.13)

No. X Y (R₅)_(s) (R₅₅)_(n) R₁₃ C.1 N OCH₃ 4-Cl n = 0 H C.2 N NHCH₃ 3-Cln = 0 H C.3 CH OCH₃ 4-Cl n = 0 H C.4 CH OCH₃ 4-Cl n = 0 CH₃ C.5 N OCH₃4-Cl n = 0 CH₃ C.6 N NHCH₃ 3-Cl n = 0 CH₃ C.7 CH OCH₃ 2-Cl n = 0 CH₂CH₃C.8 N OCH₃ 4-Cl n = 0 CH₂CH₃ C.9 N NHCH₃ 4-Cl n = 0 CH₂CH₃ C.10 N NHCH₃4-Cl n = 0 C(O)H C.11 CH OCH₃ 4-Cl n = 0 C(O)CH₃ C.12 CH OCH₃ 2,4-Cl₂ n= 0 H C.13 CH OCH₃ 2,4-Cl₂ n = 0 CH₃ C.14 N OCH₃ 2,4-Cl₂ n = 0 CH₃ C.15CH OCH₃ 2,4-Cl₂ n = 0 CH₂CH₃ C.16 N OCH₃ 2,4-Cl₂ n = 0 C(O)H C.17 CHOCH₃ 2,4-Cl₂ n = 0 C(O)CH₃ C.18 N NHCH₃ 2,4-Cl₂ n = 0 C(O)CH₃ C.19 NOCH₃ 4-CF₃ n = 0 H C.20 N NHCH₃ 4-CF₃ n = 0 H C.21 CH OCH₃ 4-CF₃ n = 0CH₃ C.22 N NHCH₃ 3-CF₃ n = 0 CH₃ C.23 CH OCH₃ 4-CF₃ n = 0 CH₂CH₃ C.24 NNHCH₃ 4-CF₃ n = 0 CH₂CH₃ C.25 CH OCH₃ 3-CF₃ n = 0 C(O)H C.26 N NHCH₃4-CF₃ n = 0 C(O)H C.27 N NHCH₃ 4-CF₃ n = 0 C(O)CH₃ C.28 CH OCH₃ 3-CF₃ n= 0 H C.29 N NHCH₃ 3-CF₃ n = 0 H C.30 CH OCH₃ 3-CF₃ n = 0 CH₂CH₃ C.31 NNHCH₃ 3-CF₃ n = 0 CH₂CH₃ C.32 N OCH₃ 3-CF₃ n = 0 C(O)H C.33 N NHCH₃3-CF₃ n = 0 C(O)CH₃ C.34 CH OCH₃ 3-Cl n = 0 H C.35 CH OCH₃ 4-NHCH₃ n = 0H C.36 CH OCH₃ 3-OCH₃ n = 0 CH₃ C.37 CH OCH₃ 3,5-Cl₂ n = 0 CH₃ C.38 CHOCH₃ 3,4-Cl₂ n = 0 iso-CH₂CH₂CH₃ C.39 CH OCH₃ 4-Br n = 0 CH₂CH₃ C.40 CHOCH₃ 4-C₆H₅ n = 0 n-CH₂CH₂CH₃ C.41 CH OCH₃ 2-CN n = 0 CH₂OCH₃ C.42 CHOCH₃ 3-NO₂ n = 0 C(O)H C.43 CH OCH₃ 3-C(O)CH₃ n = 0 C(O)C(O)CH₃ C.44 CHOCH₃ 4-NHC(O)CH₃ n = 0 C(O)C(O)OCH₃ C.45 CH OCH₃ 4-SF₅ n = 0 C(O)CH₂CH₃C.46 CH OCH₃ 3-OCF₃ n = 0 C(S)CH₃ C.47 CH OCH₃ 4-Cl n = 0 C(S)SCH₃ C.48CH OCH₃ 3-Cl 3-Cl H C.49 CH OCH₃ 4-CH₃ 2-Br H C.50 CH OCH₃ 4-NHCH₃ 2-CNH C.51 CH OCH₃ 3-OCH₃ 3-Cl CH₃ C.52 CH OCH₃ 3,5-Cl₂ 2-F CH₃ C.53 CH OCH₃3,4-Cl₂ 2-OCH₃ iso-CH₂CH₂CH₃ C.54 CH OCH₃ 4-Br 3,5-Cl₂ CH₂CH₃ C.55 CHOCH₃ 4-C₆H₅ 3-CH₃ n-CH₂CH₂CH₃ C.56 CH OCH₃ 2-CN 3,5-F₂ CH₂OCH₃ C.57 CHOCH₃ 3-NO₂ 2,3-F₂ C(O)H C.58 CH OCH₃ 3-C(O)CH₃ 3-NHCH₃ C(O)C(O)CH₃ C.59CH OCH₃ 4-NHC(O)CH₃ 3-Cl C(O)C(O)OCH₃ C.60 CH OCH₃ 4-SF₅ 2-Cl C(O)CH₂CH₃C.61 CH OCH₃ 3-OCF₃ 3-SCH₃ C(S)CH₃ C.62 CH OCH₃ 4-Cl 2,6-Cl₂ C(S)SCH₃C.63 CH OCH₃ 4-CF₃ n = 0 H C.64 CH OCH₃ 4-Cl n = 0 C(O)H C.65 CH OCH₃4-CF₃ n = 0 C(O)H C.66 CH OCH₃ 4-OCF₃ n = 0 H C.67 CH OCH₃ 4-OCF₃ n = 0C(O)H C.68 CH OCH₃ 2,4-F₂ n = 0 H C.69 N OCH₃ 3-CF₃ n = 0 H C.70 N OCH₃4-OCF₃ n = 0 H C.71 N OCH₃ 4-OCF₃ n = 0 C(O)H C.72 N OCH₃ 2,4-F₂ n = 0 HC.73 N NCH₃ 4-OCF₃ n = 0 H C.74 N NCH₃ 2,4-F₂ n = 0 H

Table 12-1: Compounds of formula 1.12 wherein AR₇ is CH₃ and thecombination of substituents X, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ for eachcompound corresponds to a line of Table C.

Compound of formula (I.12) wherein A—R₇ is methyl and the substituentsX, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ correspond to line C.4 of Table C:m.p.: 126-127° C. (compound 12-1.4).

Compound of formula (I.12) wherein A—R₇ is methyl and the substituentsX, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ correspond to line C.12 of Table C:m.p.: 132-133° C. (compound 12-1.12).

Compound of formula (I.12) wherein A—R₇ is methyl and the substituentsX, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ correspond to line C.24 of Table C:amorphous (compound 12-1.24).

Compound of formula (I.12) wherein A—R₇ is methyl and the substituentsX, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ correspond to line C.28 of Table C:m.p.: 83-84° C. (compound 12-1.28).

Compound of formula (I.12) wherein A—R₇ is methyl and the substituentsX, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ correspond to line C.29 of Table C:m.p.: 76-77° C. (compound 12-1.29).

Compound of formula (I.12) wherein A—R₇ is methyl and the substituentsX, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ correspond to line C.63 of Table C:m.p.: 83-84° C. (compound 12-1.63).

Compound of formula (I.12) wherein A—R₇ is methyl and the substituentsX, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ correspond to line C.64 of Table C:m.p.: 146-148° C. (compound 12-1.64).

Compound of formula (I.12) wherein A—R₇ is methyl and the substituentsX, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ correspond to line C.65 of Table C:m.p.: 109-110° C. (compound 12-1.65).

Compound of formula (I.12) wherein A—R₇ is methyl and the substituentsX, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ correspond to line C.32 of Table C:m.p.: 104-105° C. (compound 12-1.32).

Compound of formula (I.12) wherein A—R₇ is methyl and the substituentsX, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ correspond to line C.66 of Table C:m.p.: 74-85° C. (compound 12-1.66).

Compound of formula (I.12) wherein A—R₇ is methyl and the substituentsX, Y. (R₅)_(s), (R₅₅)_(n) and R₁₃ correspond to line C.67 of Table C:m.p.: 65-76° C. (compound 12-1.67).

Compound of formula (I.12) wherein A—R₇ is methyl and the substituentsX, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ correspond to line C.68 of Table C:m.p.: 126-127° C. (compound 12-1.68).

Compound of formula (I.12) wherein A—R₇ is methyl and the substituentsX, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ correspond to line C.70 of Table C:m.p.: 122-123° C. (compound 12-1.70).

Compound of formula (I.12) wherein A—R₇ is methyl and the substituentsX, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ correspond to line C.71 of Table C:m.p.: 58-59° C. (compound 12-1.71).

Compound of formula (I.12) wherein A—R₇ is methyl and the substituentsX, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ correspond to line C.73 of Table C:m.p.: 63-64° C. (compound 12-1.73).

Table 12-2: Compounds of formula (I.12) wherein AR₇ is CH₂CH₃ and thecombination of substituents X, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ for eachcompound corresponds to a line of Table 2.

Compound of formula (I.12) wherein A—R₇ is ethyl and the substituents X,Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ correspond to line C.24 of Table C: m.p.:56-57° C. (compound 12-2.24).

Compound of formula (I.12) wherein A—R₇ is ethyl and the substituents X,Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ correspond to line C.28 of Table C: m.p.:90-91° C. (compound 12-2.28).

Compound of formula (I.12) wherein A—R₇ is ethyl and the substituents X,Y, (R₅)_(s), (R₅₅R₆)_(n) and R₁₃ correspond to line C.29 of Table C:m.p.: 168-169° C. (compound 12-2.29).

Compound of formula (I.12) wherein A—R₇ is ethyl and the substituents X,Y, (R₅)_(s), (R₆)_(n) and R₁₃ correspond to line C.33 of Table C: m.p.:59-60° C. (compound 12-2.33).

Compound of formula (I.12) wherein A—R₇ is ethyl and the substituents X,Y, (R₅)_(s), (R₆)_(n) and R₁₃ correspond to line C.69 of Table C: resin(compound 12-2.69).

Compound of formula (I.12) wherein A—R₇ is ethyl and the substituents X,Y, (R₅)_(s), (R₆)_(n) and R₁₃ correspond to line C.70 of Table C: m.p.:132-133° C. (compound 12-2.70).

Compound of formula (I.12) wherein A—R₇ is ethyl and the substituents X,Y, (R₅)_(s), (R₆)_(n) and R₁₃ correspond to line C.71 of Table C: m.p.:131-132° C. (compound 12-2.72).

Compound of formula (I.12) wherein A—R₇ is ethyl and the substituents X,Y, (R₁₅)_(s) (R₆)_(n) and R₁₃ correspond to line C.73 of Table C: m.p.:69-70° C. (compound 12-2.73).

Compound of formula (I.12) wherein A—R₇ is ethyl and the substituents X,Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ correspond to line C.74 of Table C: m.p.:70-71° C. (compound 12-2.74).

Table 12-3: Compounds of formula (I.12) wherein AR₇ is CH₂CH═CH₂ and thecombination of substituents X, Y, (R₅)_(s), (R55)_(n) and R₁₃ for eachcompound corresponds to a line of Table 2.

Table 12-4: Compounds of formula (I.12) wherein AR₇ is CH₂C═CH and thecombination of substituents X, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ for eachcompound corresponds to a line of Table 2.

Table 12-5: Compounds of formula (I.12) wherein AR₇ is CH₂CH₂CH₃ and thecombination of substituents X, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ for eachcompound corresponds to a line of Table 2.

Table 12-6: Compounds of formula (I.12) wherein AR₇ is CH(CH₃)₂ and thecombination of substituents X, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ for eachcompound corresponds to a line of Table C. Table 12-7: Compounds offormula (I.12) wherein AR₇ is CH₂CH₂CH₂CH₃ and the combination ofsubstituents X, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ for each compoundcorresponds to a line of Table C.

Table 12-8: Compounds of formula (I.12) wherein AR₇ is CH(CH₃)(CH₂CH₃)and the combination of substituents X, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃for each compound corresponds to a line of Table C.

Table 12-9: Compounds of formula (I.12) wherein AR₇ is C(CH₃)₃ and thecombination of substituents X, Y, (R₅)_(s), (R⁵⁵)_(n) and R₁₃ for eachcompound corresponds to a line of Table C.

Table 12-10: Compounds of formula (I.12) wherein AR₇ is CH₂CF₃ and thecombination of substituents X, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ for eachcompound corresponds to a line of Table C.

Table 12-11: Compounds of formula (I.12) wherein AR₇ is CH₂CH═C(CH₃)₂and the combination of substituents X, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃for each compound corresponds to a line of Table C.

Table 12-12: Compounds of formula (I.12) wherein AR₇ is CH₂CH═CCl₂ andthe combination of substituents X, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ foreach compound corresponds to a line of Table C.

Table 12-13: Compounds of formula (I.12) wherein AR₇ is CH₂Si(CH₃)₃ andthe combination of substituents X, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ foreach compound corresponds to a line of Table C.

Table 12-14: Compounds of formula (I.12) wherein AR₇ isCH₂-c.propyl-2,2-Cl₂ and the combination of substituents X, Y, (R₅)_(s),(R₅₅)_(n) and R₁₃ for each compound corresponds to a line of Table C.

Table 12-15: Compounds of formula (I.12) wherein AR₇ is CH₂CN and thecombination of substituents X, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ for eachcompound corresponds to a line of Table C.

Table 12-16: Compounds of formula (I.12) wherein AR₇ is CH₂COOCH₃ andthe combination of substituents X, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ foreach compound corresponds to a line of Table C.

Table 12-17: Compounds of formula (I.12) wherein AR₇ is CH₂COO-iso-C₃H₇and the combination of substituents X, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃for each compound corresponds to a line of Table C.

Table 12-18: Compounds of formula (I.12) wherein AR₇ is C(═O)OC₂H₅ andthe combination of substituents X, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ foreach compound corresponds to a line of Table C.

Table 12-19: Compounds of formula (I.12) wherein AR₇ is C(═O)NHCH₃ andthe combination of substituents X, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ foreach compound corresponds to a line of Table C.

Table 12-20: Compounds of formula (I.12) wherein AR₇ is C(═O)C(═O)OC₂H₅and the combination of substituents X, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃for each compound corresponds to a line of Table C.

Table 12-21: Compounds of formula (I.12) wherein AR₇ is CH₂C₆H₅ and thecombination of substituents X, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ for eachcompound corresponds to a line of Table C.

Table 12-22: Compounds of formula (I.12) wherein AR₇ is CH₂C₆H₄-2-F andthe combination of substituents X, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ foreach compound corresponds to a line of Table C.

Table 12-23: Compounds of formula (I.12) wherein AR₇ is CH₂C₆H₄-3-Cl andthe combination of substituents X, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ foreach compound corresponds to a line of Table C.

Table 12-24: Compounds of formula (I.12) wherein AR₇ is CH₂C₆H₄-4-Br andthe combination of substituents X, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ foreach compound corresponds to a line of Table C.

Table 12-25: Compounds of formula (I.12) wherein AR₇ is CH₂C₆H₄-3-CF₃and the combination of substituents X, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃for each compound corresponds to a line of Table C.

Table 12-26: Compounds of formula (I.12) wherein AR₇ is CH₂C₆H₄-4-CF₃and the combination of substituents X, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃for each compound corresponds to a line of Table C.

Table 13-1: Compounds of formula (I.13) wherein AR₇ is CH₃ and thecombination of substituents X, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ for eachcompound corresponds to a line of Table C.

Table 13-2: Compounds of formula (I.13) wherein AR₇ is CH₂CH₃ and thecombination of substituents X, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ for eachcompound corresponds to a line of Table C.

Table 13-3: Compounds of formula (I.13) wherein AR₇ is CH₂CH≡CH₂ and thecombination of substituents X, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ for eachcompound corresponds to a line of Table C.

Table 13-4: Compounds of formula (I.13) wherein AR₇ is CH₂C≡CH and thecombination of substituents X, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ for eachcompound corresponds to a line of Table C.

Table 13-5: Compounds of formula (I.13) wherein AR₇ is CH₂CH₂CH₃ and thecombination of substituents X, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ for eachcompound corresponds to a line of Table C.

Table 13-6: Compounds of formula (I.13) wherein AR₇ is CH(CH₃)₂ and thecombination of substituents X, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ for eachcompound corresponds to a line of Table C.

Table 13-7: Compounds of formula (I.13) wherein AR₇ is CH₂CH₂CH₂CH₃ andthe combination of substituents X, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ foreach compound corresponds to a line of Table C.

Table 13-8: Compounds of formula (I.13) wherein AR₇ is CH(CH₃)(CH₂CH₃)and the combination of substituents X, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃for each compound corresponds to a line of Table C.

Table 13-9: Compounds of formula (I.13) wherein AR₇ is C(CH₃)₃ and thecombination of substituents X, Y, (R₅)_(s), (R₅₅)_(n) and R₁₃ for eachcompound corresponds to a line of Table C.

TABLE 14 Compounds of formula (I.14)

The figures in the column “Phys. data” denote melting points in ° C. No.R₅ AR₇ X Y n Phys. data 14.1 2-Cl C₂H₅ CH OCH₃ 2 oil 14.2 2-Cl C₂H₅ NOCH₃ 2 m.p. 83-85° C. 14.3 2-Cl C₂H₅ N NHCH₃ 2 oil 14.4 4-Cl C₂H₅ CHOCH₃ 2 m.p. 90-92° C. 14.5 4-Cl C₂H₅ N OCH₃ 2 m.p. 85-87° C. 14.6 4-ClC₂H₅ N NHCH₃ 2 oil 14.7 4-CF₃ C₂H₅ CH OCH₃ 2 14.8 4-CF₃ C₂H₅ N OCH₃ 214.9 4-CF₃ C₂H₅ N NHCH₃ 2 14.10 2-CF₃ C₂H₅ CH OCH₃ 2 14.11 2-CF₃ C₂H₅ NOCH₃ 2 14.12 2-CF₃ C₂H₅ N NHCH₃ 2 14.13 4-CF₃ C₂H₅ N OCH₃ 3 oil 14.144-CF₃ CH₃ CH OCH₃ 3 resin 14.15 3-CF₃ CH₃ CH OCH₃ 4 oil 14.16 4-CF₃ CH₃CH OCH₃ 4 resin 14.17 4-CF₃ C₂H₅ N OCH₃ 4 oil 14.18 3-CF₃ CH₃ CH OCH₃ 4oil 14.19 3-CF₃ C₂H₅ N OCH₃ 4 oil 14.20 3-CF₃ C₂H₅ N NHCH₃ 4 oil 14.213-CF₃ C₂H₅ N OCH₃ 3 oil 14.22 3-CF₃ C₂H₅ N NHCH₃ 3 resin

TABLE 15 Compounds of formula (I.15)

The figures in the column “Phys. data” denote melting points in ° C. No.R₅ AR₇ X Y G-T Phys. data 15.1 H C₂H₅ CH OCH₃ CH₂—CH₂ oil 15.2 H C₂H₅ NOCH₃ CH₂—CH₂ oil 15.3 H C₂H₅ N NHCH₃ CH₂—CH₂ resin 15.4 H CH₃ CH OCH₃CH₂—S oil 15.5 H CH₃ N OCH₃ CH₂—S resin 15.6 H CH₃ N NHCH₃ CH₂—S 111-11315.7 H C₂H₅ CH OCH₃ CH₂—S oil 15.8 H C₂H₅ N OCH₃ CH₂—S oil 15.9 H C₂H₅ NNHCH₃ CH₂—S resin 15.10 H CH₂C≡CH CH OCH₃ CH₂—S oil 15.11 H CH₂C≡CH NOCH₃ CH₂—S oil 15.12 H CH₂C≡CH N NHCH₃ CH₂—S resin 15.13 4-F C₂H₅ N OCH₃CH₂—CO— resin

Formulation Examples

Formulations such as emulsifiable concentrates, solutions granules,dusts, wettable powders, emulsifiable concentrates, extruder granules,coated granules and suspension concentrates are of the same kind asmentioned in EP-A-736 252, examples F1 to F10. Accordingly, the saidformulations mentioned in EP-A-736 252 are included by reference in thesubject matter of the present invention.

Biological Examples

A) Microbicidal action

Example B1: Action against Phytophthora infestans on tomatoes

a) Curative action

After a cultivation period of three weeks, tomato plants of the “RedGnome” variety are sprayed with a zoospore suspension of the fungus andincubated in a humidity chamber at 18 to 20° C. and saturated humidity.Humidifying is discontinued after 24 hours. When the plants have driedoff, they are sprayed with a mixture containing a wettable powderformulation of the test compound at a concentration of 200 ppm. Afterthe spray-coating has dried, the plants are again placed in the humiditychamber for 4 days. The number and size of the typical leaf blotchesthat have appeared after that time serve as a measure for evaluating theeffectiveness of the test compounds.

b) Preventive-systemic action

A wettable powder formulation of the test compound at a concentration of60 ppm (based on the volume of soil) is used to water the surface of thesoil in which three-week-old tomato plants of the “Red Gnome” varietyhave been potted. After a waiting period of three days, the undersidesof the leaves of the plants are sprayed with a zoospore suspension ofPhytophthora infestans. The treated plants are then placed in a sprayingcabinet for 5 days at 18 to 20° C. and saturated humidity. After thatperiod, typical leaf blotches appear, the number and size of which areused to evaluate the effectiveness of the test compounds.

Whereas infestation in untreated and infected control plants is 100%,with the compounds of Tables 1 to 15 infestation is reduced to 20% orless in both tests. In particular, with the compounds 1-4.2, 24.2, 34.2,4-1.1, 5.5, 6.3, 8.10 and 9-2.2 the infestation is still fullysuppressed even at a concentration of 20 ppm of the test compound.

Example B2: Action against Plasmopara viticola (Bert. et Curt.) (Berd.et DeToni) on vines

Vine cuttings of the “Chasselas” variety are cultivated in a greenhouseand are infected at the 10-leaf stage, on the undersides of the leaves,with a spore suspension of Plasmopara viticola. After being kept in ahumidity chamber for 24 hours, the plants are sprayed with mixturescomprising the active ingredient in concentrations of 200 ppm, 60 ppmand 20 ppm. The plants are then kept in the humidity chamber for afurther 7 days. After that time, the disease symptoms appear in thecontrol plants. The number and size of the infection sites on thetreated plants serve as a measure for evaluating the effectiveness ofthe test compounds.

In comparison with the control plants, the plants treated with compoundsof Tables 1 to 15 exhibit an infestation of 20% or less. In particular,with the compounds 1-4.2, 3-4.2, 4-1.2, 6.3, 8.10 and 9-2.2 completecurative action is still obtained even at a concentration of 20 ppm ofthe test compound.

Example B3: Action against Puccinia graminis on wheat

a) Residual-protective action

6 days after sowing, wheat plants are sprayed to drip point with anaqueous spray mixture (0.02% active ingredient), and infected 24 hourslater with a uredospore suspension of the fungus. After an incubationperiod of 48 hours (conditions: 95 to 100% relative humidity at 20° C.),the plants are placed in a greenhouse at 22° C. Evaluation of rustpustule development is made 12 days after infection.

b) Systemic action

Wheat plants are watered 5 days after sowing with an aqueous spraymixture (0.006% active ingredient, based on the volume of soil). Care istaken that the spray mixture does not come into contact with the partsof the plants above the soil. The treated plants are infected 48 hourslater with a uredospore suspension of the fungus. After an incubationperiod of 48 hours (conditions: 95 to 100% relative humidity at 20° C.), the plants are placed in a greenhouse at 22° C. Evaluation of rustpustule development is made 12 days after infection.

The compounds of Tables 1 to 15 bring about a distinct reduction in thefungus infestation, in some cases to from 10 to 0%. In particular, withthe compounds 3-4.2, 4.1-1, 5.4, 8.10, 12-1.3, 10-1.16 and 12-1.4 thedisease is suppressed completely (0-5% infestation).

Example B4: Action against Pyricularia oryzae on rice plants

a) Residual-protective action

After a cultivation period of 2 weeks, rice plants are sprayed to drippoint with an aqueous spray mixture (0.02% active ingredient), and areinfected 48 hours later with a conidia suspension of the fungus.Evaluation of fungus infestation is made 5 days after infection, duringwhich period 95 to 100% relative humidity and a temperature of 22° C.are maintained.

b) Systemic action

2-week-old rice plants are watered with an aqueous spray mixture (0.006%active ingredient, based on the volume of soil). Care is taken that thespray mixture does not come into contact with the parts of the plantabove the soil. The pots are then filled with water so that thelowermost parts of the stems of the rice plants stand in water. After 96hours, the plants are infected with a conidia suspension of the fungusand kept for 5 days at 95 to 100% relative humidity and a temperature of24° C.

The compounds of Tables 1 to 15 largely prevent the disease frombreaking out on the infected plants.

Example B5: Action against Erysiphe graminis on barley

) Residual-protective action

Barley plants about 8 cm in height are sprayed to drip point with anaqueous spray mixture (0.02% active ingredient) and dusted 3 to 4 hourslater with conidia of the fungus. The infected plants are placed in agreenhouse at 22° C. The fungus infestation is evaluated 10 days afterinfection.

b) Systemic action

Barley plant s about 8 cm in height are watered with an aqueous spraymixture (0.002% active ingredient, based on the volume of soil). Care istaken that the spray mixture does not come into contact With the partsof the plants above the soil. The treated plants are dusted 48 hourslater with conidia of the fungus. The infected plants are placed in agreenhouse at 22° C. The fungus infestation is evaluated 10 days afterinfection.

The compounds of Tables 1 to 15 in general are able to suppressinfestation with the disease to less than 20% and, in some cases, tosuppress it completely.

Example B6: Action against Botryis cinerea on apple fruits,Residual-protective action

Artificially damaged apples are treated by applying drops of a spraymixture (0.02% active ingredient) onto the damage sites. The treatedfruits are then inoculated with a spore suspension of the fungus andincubated for one week at high humidity and about 20° C. The fungicidalaction of the test compound is derived from the number of rotted damagesites.

Compounds of Tables 1 to 15 are able to prevent the rot from spreading,in some cases completely.

B. Insecticidal action

Example B7: Action against Aphis craccivora

Pea seedlings are infested with Aphis craccivora, subsequently sprayedwith a spray mixture comprising 100 ppm of the test compound and thenincubated at 20° C. 3 and 6 days later the percentage reduction inpopulation (% activity) is determined by comparing the number of deadaphids on the treated plants with that on untreated plants.

The compounds of Tables 1 to 15 generally exhibit good activity in thistest. In particular, compounds 1-4.2, 4.2, 34.2, 4-1.3, 4-1.7, 5.1, 5.3and 8.10 are more than 80% effective in this test.

Example B8: Action against Diabrotica balteata

Maize seedlings are sprayed with an aqueous emulsion spray mixturecomprising 100 ppm of the test compound. After the spray-coating hasdried, the maize seedlings are populated with 10 Diabrotica balteatalarvae in the second stage and then placed in a plastics container. 6days later, the percentage reduction in population (% activity) isdetermined by comparing the number of dead larvae on the treated plantswith that on untreated plants. The compounds of Tables 1 to 15 exhibitgood activity in this test. In particular, compounds 1-4.2, 2-4.2,4-1.2, 4-1.8, 5.5, 9-2.2, 12-1.3, 10-1.16 and 12-1.4 are more than 80%effective in this test.

Example B9: Action against Heliothis virescens

Young soybean plants are sprayed with an aqueous emulsion spray mixturecomprising 100 ppm of the test compound. After the spray-coating hasdried, the plants are populated with 10 Heliothis virescens caterpillarsin the first stage and then placed in a plastics container. 6 dayslater, the percentage reduction in population and the percentagereduction in feeding damage (% activity) are determined by comparing thenumber of dead caterpillars and the feeding damage on the treated plantswith that on untreated plants. Most compounds of Tables 1 to 15 exhibitgood activity in this test. In particular, compound 5.1 is more than 80%effective in this test Example B10: Action against Spodoptera littoralis

Young soybean plants are sprayed with an aqueous emulsion spray mixturecomprising 100 ppm of the test compound. After the spray-coating hasdried, the plants are populated with 10 Spodoptera littoraliscaterpillars in the third stage and then placed in a plastics container.3 days later, the percentage reduction in population and the percentagereduction in feeding damage (% activity) are determined by comparing thenumber of dead caterpillars and the feeding damage on the treated plantswith that on untreated plants. The compounds of Tables 1 to 15 exhibitgood activity in this test.

C. Acarcidal action

Example B11: Action against Tetranychus urticae

Young bean plants are populated with a mixed population of Tetranychusurticae and sprayed one day later with an aqueous emulsion spray mixturecomprising 100 ppm of the test compound. The plants are then incubatedfor 6 days at 25° C. and subsequently evaluated. The percentagereduction in population (% activity) is determined by comparing thenumber of dead eggs, larvae and adults on the treated plants with thaton untreated plants. The compounds of Tables 1 to 15 generally exhibitgood activity in this test. In particular, compounds 1-4.2, 2-4.2,3-4.2, 4-1.1, 5.5, 6.3, 8.10, 9-2.2, 12-1.3, 10-1.16 and 12-1.4 are morethan 80% effective in this test

What is claimed is:
 1. A compound of formula

wherein either X is CH or N, Y is OR₁ and Z is O, or X is N, Y is NHR₈and Z is O, S or S(═O); R₁ is hydrogen or C₁-C₄alkyl; R₈ is hydrogen orC₁-C₄alkyl; R₂ is H, C₁-C₄alkyl, halo-C₁-C₄alkyl, C₆cycloalkyl,C₁-C₄alkoxymethyl, C₁-C₄alkoxy, halo-C₁-C₄alkoxy, C₁-C₄alkylthio, haloC-C₄alkylthio or CN; R₃ and R₄ are each independently of the other H,C₁-C₄alkyl, C₁-C₄alkoxy, OH, CN, NO₂, a (C₁-C₄alkyl)₃—Si group, thealkyl groups being the same or different, halogen,(C₁-C₄alkyl)S(═O)_(m), (halo-C₁-C₄alkyl)S(═O)_(m), halo-C₁-C₄alkyl orhalo-C₁-C₄alkoxy; m is 0, 1 or 2; R₅ independently of any other ishalogen, C₁-C₆-alkyl, halo-C₁-C₆alkyl, C₃-C₆-cycloalkyl,halo-C₃-C₆cycloalkyl, C₁-C₆alkoxy, halo-C₁-C₆alkoxy, C₁-C₆-alkylthio,halo-C₁-C₆-alkylthio, C₁-C₆alkylsulfinyl, halo-C₁-C₆alkylsulfinyl,C₁-C₆alkylsulfonyl, halo-C₁-C₆alkylsulfonyl, C₁-C₆alkylsulfonyloxy,halo-C₁-C₆alkylsulfonyloxy, C₁-C₆alkoxy-C₁-C₆alkyl,halo-C₁-C₆alkoxy-C₁-C₆alkyl, C₁-C₆alkylthio-C₁-C₆alkyl,halo-C₁-C₆alkylthio-C₁-C₆alkyl, C₁-C₆alkylsulfinyl-C₁-C₆alkyl,halo-C₁-C₆alkylsulfinyl-C₁-C₆alkyl, C₁-C₆alkylsulfonyl-C₁-C₆alkyl,halo-C₁-C₆alkylsulfonyl-C₁-C₆alkyl, C₁-C₆alkylcarbonyl,halo-C₁-C₆alkylcarbonyl, C₁-C₆alkoxycarbonyl, halo-C₁-C₆alkoxycarbonyl,C₁-C₆alkylaminocarbonyl, C₁-C₄alkoxyiminomethyl,di(C₁-C₆alkyl)aminocarbonyl, the alkyl groups being the same ordifferent; C₁-C₆alkylaminothiocarbonyl, di(C₁-C₆alkylaminothiocarbonyl,the alkyl groups being the same or different; C₁-C₆alkylamino,di(C₁-C₆alkyl)amino, the alkyl groups being the same or different; NO₂,CN, SF₅, thioamido, thiocyanatomethyl, trimethylsilyl;C₁-C₄alkylenedioxy or —CH═CH—CH═CH- each of which is unsubstituted or,depending on its substitution possibilities, mono- to tetra-substituted,the substituents of the C₁-C₄alkylenedioxy or —CH═CH—CH═CH— group beingselected from the group consisting of C₁-C₄alkyl and halogen; aryl-Q,heterocyclyl , aryl-Q—C₁-C₆alkyl, aryl-Q—C₂C₆alkenyl,heterocyclyl-C₁-C₆alkyl or heterocyclyl-Q—C₂-C₆alkenyl, or aryl-Q—,heterocyclyl-Q—, aryl-Q—C₁-C₆alkyl, aryl-C₂-C₆alkenyl,heterocyclyl(C₁-C₆alkyl or heterocyclyl-Q—C₂-C₂alkenyl each of which is,depending on its substitution possibilities, mono- to penta-substitutedin the aryl or heterocyclyl ring, the substituents being selectedindependently of one another from the group consisting of halogen,C₁-C₆alkyl, halo-C₁-C₆alkyl, C₃-C₆cycloalkyl, halo-C₃-C₆cycloalkyl,C₁-C₆alkoxy, halo-C₁-C₆alkoxy, CN, nitro and C₁-C₆alkoxycarbonyl; and,when n is greater than 1, the radicals R₅ are the same or different; nis 0, 1, 2, 3 or, if either a or b is 0, the n may also be 4; Q is adirect bond, —CH(OH), —C(═O), —S—, —S(═O) or —S(═O)₂; R₉ is methyl,fluoromethyl or difluoromethyl; either A is a direct bond,C₁-C₁₀alkylene, —C(═O)—, —C(═S)— or halo-C₁-C₁₀alkylene and R₇ is aradical R₁₀; or A is C₁-C₁₀alkylene, —C(═O)—, —C(═S) orhalo-C₁-C₁₀alkylene and R₇ is —CN, OR₁₀, N(R₁₀)₂, the radicals R₁₀ beingthe same or different, —SR₁₀, —S(═O)R₁₀ or —S(═O)₂R₁₀; R₁₀ is H,C₁-C₆alkyl, C₂-C₈alkenyl, C₂C₈alkynyl or C₃-C₆cycloalkyl, or C₁-C₆alkyl,C₂-C₈alkenyl, C₂-C₈alkynyl or C₃-C₆cycloalkyl each mono- orpoly-substituted by substituents from the group consisting of halogen;—Si(C₁-C₄alkyl)₃, the alkyl groups being the same or different;C₁-C₄alkoxycarbonyl or an aryl or heterocyclyl group that isunsubstituted or mono- or poly-substituted by substituents selected fromthe group consisting of halogen, C₁-C₄alkyl and halo-C₁-C₄alkyl; and Dis O, S, —S(═O) or S(═O)₂; G is —CH(CH₃)—; T—R₆ is R₆;—C(═N—O—A₁—R₇₇)R₈; —SiR₁₄(R₁₅)—R₆; —C(═O)—R₆; —C(R₁₆)═C(R₁₇)—R₆; C≡C—R₆or —D—R₆; R₆ is C₁-C₄alkyl, aryl or heteroaryl; or aryl or heteroaryleach of which is 0, 1, 2, 3, 4 or 5, the substituents R₅ beingindependent of one another when s is greater than 1; A₁ and R₇₇ are asdefined above for A and R₇; a is 0 or 1; L is U—R₁₈, P(O)_(v)R₁₁R₁₂,P(S)_(w)R₁₁R₁₂ or N(aryl)R₁₃, the aryl radical being eitherunsubstituted or mono- to penta-substituted by substituents selectedindependently of one another from the group consisting of R₅; v and ware0 or 1; U—R₁₈ is —C(═O)—C(═O)—R₁₈; —C(OH)—C(OH)—R₁₈; —C(═N—O—A₁—R₇)—R₁₈;

p is from 0 to 4; R₁₁ and R₁₂ are each independently of the otherC₁-C₆alkyl, halo-C₁-C₆alkyl, C₃-C₆cycloalkyl, halo-C₃-C₆cycloalkyl,C₁-C₆alkoxy, halo-C₁-C₆alkoxy, C₁-C₆alkylthio, halo-C₁-C₆alkylthio,aryl, heteroaryl, aryloxy, arylthio, heteroaryloxy or heteroarylthio; oraryl, heteroaryl, aryloxy, arylthio, heteroaryloxy or heteroarylthioeach mono- to penta-substituted by R₅, the substituents R₅ beingindependent of one another; b is 0 or 1, but a and b are notsimultaneously 0; R₁₃ is hydrogen, C₁-C₆alkyl, halo-C₁-C₆alkyl,C₃-C₆cycloalkyl, halo-C₃-C₆cycloalkyl, C₁-C₆alkylsulfinyl,halo-C₁-C₆alkylsulfinyl, C₁-C₆alkylsulfonyl, halo-C₁-C₆alkylsulfonyl,C₁-C₆alkoxy-C₁-C₆alkyl, halo-C₁-C₆alkoxy-C₁-C₆alkyl,C₁-C₆alkylthio-C₁-C₆alkyl, halo-C₁-C₆alkylthio-C₁-C₆alkyl,C₁-C₆alkylsulfinyl-C₁-C₆alkyl, halo-C₁-C₆alkylsulfinyl-C₁-C₆alkyl,C₁-C₆alkylsulfonyl-C₁-C₆alkyl, halo-C₁-C₆alkylsulfonyl-C₁-C₆alkyl,formyl, C₁-C₆alkylcarbonyl, C₁-C₆alkyl-C(═S)—, C₁-C₆alkylthio-C(═S)—,halo-C₁-C₆alkylcarbonyl, C₁-C₆alkoxycarbonyl, halo-C₁-C₆alkoxycarbonyl,C₁-C₆alkylaminocarbonyl, C₁-C₄-alkoxyiminomethyl,di(C₁-C₆alkyl)aminocarbonyl, the alkyl groups being the same ordifferent; C₁-C₆alkylaminothiocarbonyl, di(C₁-C₆alkyl)aminothiocarbonyl,the alkyl groups being the same or different; C₁-C₆alkydicarbonyl,halo-C₁-C₆alkyldicarbonyl, C₁-C₆alkoxydicarbonyl,halo-C₁-C₆alkoxydicarbonyl, C₁-C₆alkylaminodicarbonyl,di(C₁-C₆alkyl)aminodicarbonyl, the alkyl groups being the same ordifferent; C₁-C₆alkylaminodithiocarbonyl,di(C₁-C₆alkylaminodithiocarbonyl, the alkyl groups being the same ordifferent; aryl, arylsulfinyl, aryl-C₁-C₆alkylsulfinyl, arylsulfonyl,aryl-C₁-C₆alkyl-sulfonyl, aryloxy-C₁-C₆alkyl, arylthio-C₁-C₆alkyl,aryl-C₁-C₆alkylsulfinyl-C₁-C₆alkyl, aryl-C₁-C₆alkylsulfonyl-C₁-C₆alkyl,arylcarbonyl, arylalkylcarbonyl, aryloxycarbonyl, arylalkoxycarbonyl,arylaminocarbonyl, aryloxyiminomethyl, di(aryl)aminocarbonyl, the arylgroups being the same or different arylaminothiocarbonyl,di(aryl)aminothiocarbonyl, the aryl groups being the same or different;aryldicarbonyl, aryl-C₁-C₆alkyldicarbonyl, aryloxydicarbonyl,aryl-C₁-C₆alkoxydicarbonyl, arylaminodicarbonyl,di(aryl)aminodicarbonyl, the aryl groups being the same or different;arylaminodithiocarbonyl, di(arylaminodithiocarbonyl, the aryl groupsbeing the same or different; and the aryl groups in the afore-mentionedsubstituents being unsubstituted or mono- to penta-substituted bysubstituents R₅, the substituents R₅ being independent of one another,unsubstituted or substituted heteroaryl, unsubstituted or substitutedheteroarylcarbonyl, unsubstituted or substituted heteroarylsulfinyl, orunsubstituted or substituted heteroarylsulfonyl; R₁₄ and R₁₅ are eachindependently of the other C₁C₄-alkyl; R₁₆ and R₁₇ are eachindependently of the other hydrogen, C₁-C₄alkyl or halogen and R₁₈ isR₆; and their possible E/Z isomers, mixtures of E/Z isomers and/ortautomers, in each case in free form or in salt form.
 2. The compoundaccording to claim 1 of formula (I) in free form.
 3. The compoundaccording to claim 2 of formula (I) wherein X is CH and Z is O.
 4. Thecompound according to claim 2 of formula (I) wherein X is N and Z is O.5. The compound according to claim 2 of formula (I) wherein Y isOC₁-C₄alkyl.
 6. The compound according to claim 1 of the formula:

X is N; Y is methoxy; AR⁷ is ethyl; R is methyl; and R⁵ is 4-CF₃.
 7. Thecompound according to claim 3 of formula (I) wherein R₂ is H, C₁-C₄alkylor C₃-C₆cycloalkyl.
 8. The compound according to claim 3 of formula (I)wherein R₃ is H, C₁-C₄alkyl, C₁-C₄alkoxy, OH, CN, NO₂, halogen,halo-C₁-C₄alkyl or halo-C₁-C₄alkoxy.
 9. The compound according to claim3 of formula (I) wherein R₄ is H, C₁-C₄alkyl, C₁-C₄alkoxy, OH, CN, NO₂,halogen, halo-C₁-C₄alkyl or halo-C₁-C₄alkoxy.
 10. The compound accordingto claim 3 of formula (I) wherein R₈ is H or C₁-C₂alkyl.
 11. Thecompound according to claim 3 of formula (I) wherein R₉ is methyl orfluoromethyl.
 12. The compound according to claim 3 of formula (I)wherein A is a direct bond, C₁-C₁₀alkylene or halo C₁-C₁₀alkylene, andR₇ is a radical R₁₀.
 13. The compound according to claim 12 of formula(I) wherein AR₇ is methyl or ethyl.
 14. The compound according to claim3 of formula (I) wherein a is 1, n is 0, b is 0 and D is oxygen.
 15. Thecompound according to claim 14 of formula (I) wherein a is 1 and G isC₁-C₄alkylene.
 16. The compound according to claim 3 of formula (I)wherein R₆ is C₁-C₄alkyl, aryl, or arylmono- to penta-substituted bysubstituents selected independently of one another from the groupconsisting of R₅.